Showing 1–50 of 105 results for author: Smith, E

Mapping vacancy and bonding electron distributions around aluminium nanovoids

Authors: Philip N. H. Nakashima, Yu-Tsun Shao, Zezhong Zhang, Andrew E. Smith, Tianyu Liu, Nikhil V. Medhekar, Joanne Etheridge, Laure Bourgeois, Jian-Min Zuo

Abstract: All materials have defects and many contain nanostructures, both of which disrupt chemical bonding - the basis of materials properties. No experimental measurements of bonding electron distributions associated with defects and nanostructures have ever been possible. We present a method enabling such measurements and interrogate nanovoids surrounded by vacancies - the most fundamental of nanostruct… ▽ More All materials have defects and many contain nanostructures, both of which disrupt chemical bonding - the basis of materials properties. No experimental measurements of bonding electron distributions associated with defects and nanostructures have ever been possible. We present a method enabling such measurements and interrogate nanovoids surrounded by vacancies - the most fundamental of nanostructures and defects - in aluminium. We measure the volume of a vacancy with 3% uncertainty and map vacancy concentrations surrounding nanovoids with nanometre resolution in three dimensions where previously only two-dimensional mapping was possible. We discover that radiation-damaged voids can "heal". Our bonding measurements are depth-resolved, vacancy-sensitive, and agree with density functional theory. This work opens bonding electron density measurements to inhomogeneous nanostructured multi-phased materials so that the electronic origins of phenomena such as strengthening, weakening, interface functionality, solute diffusion and phase transformations within them may be revealed. △ Less

Submitted 4 December, 2025; originally announced December 2025.

Comments: 69 pages, 4 main figures, 11 extended data figures, 9 supplementary figures, 1 main table, 1 supplementary table, 96 references

The influence of boundary conditions and interfacial slip on the time taken to achieve a nonequilibrium steady-state for highly confined flows

Authors: Carmelo Riccardo Civello, Luca Maffioli, Joseph Johnson, Edward R. Smith, James P. Ewen, Peter J. Daivis, Daniele Dini, B. D. Todd

Abstract: We investigate the equilibration time to attain steady-state for a system of liquid molecules under boundary-driven planar Couette flow via nonequilibrium molecular dynamics (NEMD) simulation. In particular, we examine the equilibration time for the two common types of boundary driven flow: one in which both walls slide with equal and opposite velocity, and the other in which one wall is fixed and… ▽ More We investigate the equilibration time to attain steady-state for a system of liquid molecules under boundary-driven planar Couette flow via nonequilibrium molecular dynamics (NEMD) simulation. In particular, we examine the equilibration time for the two common types of boundary driven flow: one in which both walls slide with equal and opposite velocity, and the other in which one wall is fixed and the other moves with twice the velocity. Both flows give identical steady-state strain rates, and hence flow properties, but the transient behaviour is completely different. We find that in the case of no-slip boundary conditions, the equilibration times for the counter-sliding walls flow are exactly 4 times faster than those of the single sliding wall system, and this is independent of the atomistic nature of the fluid, i.e., it is an entirely hydrodynamic feature. We also find that systems that exhibit slip have longer equilibration times in general and the ratio of equilibration times for the two types of boundary-driven flow is even more pronounced. We analyse the problem by decomposing a generic planar Couette flow into a linear sum of purely symmetric and antisymmetric flows. We find that the no-slip equilibration time is dominated by the slowest decaying eigenvalue of the solution to the Navier-Stokes equation. In the case of slip, the longest relaxation time is now dominated by the transient slip velocity response, which is longer than the no-slip response time. In the case of a high-slip system of water confined to graphene channels, the enhancement is over two orders of magnitude. △ Less

Submitted 25 September, 2025; originally announced September 2025.

Comments: 29 pages, 12 figures

Experimental validation of electron correlation models in warm dense matter

Authors: Dmitrii S. Bespalov, Ulf Zastrau, Zhandos A. Moldabekov, Thomas Gawne, Tobias Dornheim, Moyassar Meshhal, Alexis Amouretti, Michal Andrzejewski, Karen Appel, Carsten Baehtz, Erik Brambrink, Khachiwan Buakor, Carolina Camarda, David Chin, Gilbert Collins, Celine Crepisson, Adrien Descamps, Jon Eggert, Luke Fletcher, Alessandro Forte, Gianluca Gregori, Marion Harmand, Oliver S. Humphries, Hauke Hoeppner, Jonas Kuhlke , et al. (37 additional authors not shown)

Abstract: We report X-ray Thomson scattering measurements of warm dense aluminium at densities 3.75-4.5 g/cm$^3$ and a temperature of approximately 0.6 eV, performed at the HED-HiBEF instrument of the European XFEL using the DiPOLE-100X drive laser. By probing plasmon dispersion across momentum transfers $k$ = 0.99-2.57 Angstrom$^{-1}$ with high statistical fidelity, we directly test competing theories of e… ▽ More We report X-ray Thomson scattering measurements of warm dense aluminium at densities 3.75-4.5 g/cm$^3$ and a temperature of approximately 0.6 eV, performed at the HED-HiBEF instrument of the European XFEL using the DiPOLE-100X drive laser. By probing plasmon dispersion across momentum transfers $k$ = 0.99-2.57 Angstrom$^{-1}$ with high statistical fidelity, we directly test competing theories of electron dynamics under extreme conditions. Time-dependent density functional theory (TDDFT) reproduces both the observed plasmon energies and spectral shapes across the full $k$ range, whereas the random phase approximation (RPA) and static local-field-correction (LFC) models systematically overestimate the plasmon frequency, even for aluminium (a canonical uniform electron gas metal). Considering electron localisation around ions and the loss of crystalline symmetry due to liquid-state disorder, our measurements provide direct evidence that simple uniform electron gas models fail in warm dense matter and establish TDDFT as a reliable approach for electronic correlations in this regime. △ Less

Submitted 12 September, 2025; originally announced September 2025.

Comments: 25 pages, 12 figures

Magnetization and magnetostriction measurements of the dipole-octupole quantum spin ice candidate Ce2Hf2O7

Authors: Edwin Kermarrec, Guanyue Chen, Hiromu Okamoto, Chun-Jiong Huang, Han Yan, Jian Yan, Hikaru Takeda, Yusei Shimizu, Evan M. Smith, Avner Fitterman, Andrea D. Bianchi, Bruce D. Gaulin, Minoru Yamashita

Abstract: We investigate the magnetization and the magnetostriction of the dipole-octupole quantum spin ice candidate Ce2Hf2O7 down to 50 mK. We find that the magnetization curves observed with the magnetic field applied along all the principal axes ([100], [110], and [111]) exhibit a magnetic hysteresis below around 300 mK. In addition, a kink-like feature is observed in the magnetization under B || [111],… ▽ More We investigate the magnetization and the magnetostriction of the dipole-octupole quantum spin ice candidate Ce2Hf2O7 down to 50 mK. We find that the magnetization curves observed with the magnetic field applied along all the principal axes ([100], [110], and [111]) exhibit a magnetic hysteresis below around 300 mK. In addition, a kink-like feature is observed in the magnetization under B || [111], at which the magnetostriction also shows a convex field dependence. Our classical Monte-Carlo and quantum exact diagonalization calculations demonstrate that these features in the magnetization are well reproduced by the spin Hamiltonian with a dominant interaction between the octupole moments and with a QSI ground state, indicating the emergence of a dipole-octupole QSI in this compound. △ Less

Submitted 11 September, 2025; originally announced September 2025.

Comments: 10 pages, 4 figures, 1 table, and Supplementary Materials

Thermodynamic ranking of pathways in reaction networks

Authors: Praful Gagrani, Nino Lauber, Eric Smith, Christoph Flamm

Abstract: One of the puzzles left open by energetic analyses of irreversible stochastic processes is that boundary conditions that prevent the performance of work or the dissipation of heat make no contribution to an entropy-production budget; yet we see ubiquitously in both engineered and living systems that both transient and persistent energy costs are paid to create and maintain such boundaries. We wish… ▽ More One of the puzzles left open by energetic analyses of irreversible stochastic processes is that boundary conditions that prevent the performance of work or the dissipation of heat make no contribution to an entropy-production budget; yet we see ubiquitously in both engineered and living systems that both transient and persistent energy costs are paid to create and maintain such boundaries. We wish to know whether there are inherent limits for the costs of such phenomena, and common units in which those can be traded off against more familiar costs measured in terms of heat dissipation. We give this problem a concrete framing in the context of CRNs, for the problem of extracting a topologically restricted pathway from a larger distributed network, through activation of some reactions and selective elimination of others. We define a thermodynamic cost function for pathways derived from large-deviation theory of stochastic CRNs, which decomposes into two components: an ongoing maintenance cost to sustain a NESS, and a restriction cost, quantifying the ongoing improbability of neutralizing reactions outside the specified pathway. Applying this formalism to detailed-balanced CRNs in the linear response regime, we make use of their formal equivalence to electrical circuits. We prove that the resistance of a CRN decreases as reactions are added that support the throughput current, and that the maintenance cost, the restriction cost, and the thermodynamic cost of nested pathways are bounded below by those of their hosting network. For small CRNs, we show how catalytic and inhibitory mechanisms can drastically alter pathway costs, enabling unfavorable pathways to become favorable and approach the cost of the hosting pathway. Our results provide insights into the thermodynamic principles governing open CRNs and offer a foundation for understanding the evolution of metabolic networks. △ Less

Submitted 29 October, 2025; v1 submitted 29 June, 2025; originally announced June 2025.

Comments: 57 pages, 11 figures

Influence of X-ray Irradiation on the Magnetic and Structural Properties of Gadolinium Silicide Nanoparticles for Self-Regulating Hyperthermia

Authors: Samantha E. Smith, Santiago Bermudez, Pavan Chaitanya, Zoe Boekelheide, Jessika Rojas Marin, Ravi L. Hadimani

Abstract: Magnetic hyperthermia treatment (MHT) utilizes heat generated from magnetic nanoparticles (MNPs) under an alternating magnetic field (AMF) for therapeutic applications. Gadolinium silicide (Gd5Si4) has emerged as a promising MHT candidate due to its self-regulating heating properties and potential biocompatibility. However, the impact of high-dose X-ray irradiation on its magnetic behavior remains… ▽ More Magnetic hyperthermia treatment (MHT) utilizes heat generated from magnetic nanoparticles (MNPs) under an alternating magnetic field (AMF) for therapeutic applications. Gadolinium silicide (Gd5Si4) has emerged as a promising MHT candidate due to its self-regulating heating properties and potential biocompatibility. However, the impact of high-dose X-ray irradiation on its magnetic behavior remains uncertain. This study examines Gd5Si4 nanoparticles exposed to 36 and 72 kGy X-ray irradiation at a high-dose rate (120 Gy/min). While X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy confirm no structural or compositional changes, transmission electron microscopy reveals localized lattice distortions, along with observable changes in magnetic properties, as evidenced in magnetization vs. temperature and hysteresis measurements. Despite this, magnetocaloric properties and specific loss power (SLP) remain unaffected. Our findings confirm the stability of Gd5Si4 under high-dose X-ray irradiation, supporting its potential for radiotherapy (RT) and magnetocaloric cooling in deep-space applications. △ Less

Submitted 30 May, 2025; originally announced June 2025.

Two-Peak Heat Capacity Accounts for $R\ln(2)$ Entropy and Ground State Access in the Dipole-Octupole Pyrochlore Ce$_2$Hf$_2$O$_7$

Authors: E. M. Smith, A. Fitterman, R. Schäfer, B. Placke, A. Woods, S. Lee, S. H. -Y. Huang, J. Beare, S. Sharma, D. Chatterjee, C. Balz, M. B. Stone, A. I. Kolesnikov, A. R. Wildes, E. Kermarrec, G. M. Luke, O. Benton, R. Moessner, R. Movshovich, A. D. Bianchi, B. D. Gaulin

Abstract: Magnetic heat capacity measurements of a high-quality single crystal of the dipole-octupole pyrochlore Ce$_2$Hf$_2$O$_7$ down to a temperature of $T = 0.02$ K are reported. These show a two-peaked structure, with a Schottky-like peak at $T_1 \sim 0.065$ K, similar to what is observed in its sister Ce-pyrochlores Ce$_2$Zr$_2$O$_7$ and Ce$_2$Sn$_2$O$_7$. However, a second sharper peak is observed at… ▽ More Magnetic heat capacity measurements of a high-quality single crystal of the dipole-octupole pyrochlore Ce$_2$Hf$_2$O$_7$ down to a temperature of $T = 0.02$ K are reported. These show a two-peaked structure, with a Schottky-like peak at $T_1 \sim 0.065$ K, similar to what is observed in its sister Ce-pyrochlores Ce$_2$Zr$_2$O$_7$ and Ce$_2$Sn$_2$O$_7$. However, a second sharper peak is observed at $T_2 \sim 0.025$ K, signifying the entrance to the ground state. The ground state appears to have gapped excitations, as even the most abrupt extrapolation to $C_P=0$ at $T = 0$ K fully accounts for the $R\ln(2)$ entropy associated with the pseudospin-1/2 doublet for Ce$^{3+}$ in this environment. The ground state could be conventionally ordered, although theory predicts a much larger anomaly in $C_P$ at much higher temperatures than the measured $T_2$ for expectations from an all-in all-out ground state of the XYZ Hamiltonian for Ce$_2$Hf$_2$O$_7$. The sharp low-temperature peak could also signify a cross-over from a classical spin liquid to a quantum spin liquid (QSL). For both scenarios, comparison of the measured $C_P$ with NLC calculations suggests that weak interactions beyond the nearest-neighbor XYZ Hamiltonian become relevant below $T \sim 0.25$ K. The diffuse magnetic neutron scattering observed from Ce$_2$Hf$_2$O$_7$ at low temperatures between $T_2$ and $T_1$ resembles that observed from Ce$_2$Zr$_2$O$_7$, which is well established as a $π$-flux quantum spin ice (QSI). Together with the peak in the heat capacity at $T_2$, this diffuse scattering from Ce$_2$Hf$_2$O$_7$ is suggestive of a classical spin liquid regime above $T_2$ that is distinct from the zero-entropy quantum ground state below $T_2$. △ Less

Submitted 30 July, 2025; v1 submitted 14 January, 2025; originally announced January 2025.

Comments: Main Text (6 pages, 4 figures), Supplemental Material (14 pages, 17 figures)

Journal ref: Physical Review Letters 135, 086702 (2025)

Mechanical and thermodynamic routes to the liquid-liquid interfacial tension and mixing free energy by molecular dynamics

Authors: Rei Ogawa, Hiroki Kusudo, Takeshi Omori, Edward R. Smith, Laurent Joly, Samy Merabia, Yasutaka Yamaguchi

Abstract: In this study, we carried out equilibrium molecular dynamics (EMD) simulations of the liquid-liquid interface between two different Lennard-Jones components with varying miscibility, where we examined the relation between the interfacial tension and isolation free energy using both a mechanical and thermodynamic approach. Using the mechanical approach, we obtained a stress distribution around a qu… ▽ More In this study, we carried out equilibrium molecular dynamics (EMD) simulations of the liquid-liquid interface between two different Lennard-Jones components with varying miscibility, where we examined the relation between the interfacial tension and isolation free energy using both a mechanical and thermodynamic approach. Using the mechanical approach, we obtained a stress distribution around a quasi-one-dimensional (1D) EMD systems with a flat LL interface. From the stress distribution, we calculated the liquid-liquid interfacial tension based on Bakker's equation, which uses the stress anisotropy around the interface, and measures how it varies with miscibility. The second approach uses thermodynamic integration by enforcing quasi-static isolation of the two liquids to calculate the free energy. This uses the same EMD systems as the mechanical approach, with both extended dry-surface and phantom-wall (PW) schemes applied. When the two components were immiscible, the interfacial tension and isolation free energy were in good agreement, provided all kinetic and interaction contributions were included in the stress. When the components were miscible, the values were significantly different. From the result of PW for the case of completely mixed liquids, the difference was attributed to the additional free energy required to separate the binary mixture into single components against the osmotic pressure prior to the complete detachment of the two components, i.e., the free energy of mixing. △ Less

Submitted 16 September, 2024; originally announced September 2024.

Comments: 5 figures

Shock-driven amorphization and melt in Fe$_2$O$_3$

Authors: Céline Crépisson, Alexis Amouretti, Marion Harmand, Chrystèle Sanloup, Patrick Heighway, Sam Azadi, David McGonegle, Thomas Campbell, David Alexander Chin, Ethan Smith, Linda Hansen, Alessandro Forte, Thomas Gawne, Hae Ja Lee, Bob Nagler, YuanFeng Shi, Guillaume Fiquet, François Guyot, Mikako Makita, Alessandra Benuzzi-Mounaix, Tommaso Vinci, Kohei Miyanishi, Norimasa Ozaki, Tatiana Pikuz, Hirotaka Nakamura , et al. (6 additional authors not shown)

Abstract: We present measurements on Fe$_2$O$_3$ amorphization and melt under laser-driven shock compression up to 209(10) GPa via time-resolved in situ x-ray diffraction. At 122(3) GPa, a diffuse signal is observed indicating the presence of a non-crystalline phase. Structure factors have been extracted up to 182(6) GPa showing the presence of two well-defined peaks. A rapid change in the intensity ratio o… ▽ More We present measurements on Fe$_2$O$_3$ amorphization and melt under laser-driven shock compression up to 209(10) GPa via time-resolved in situ x-ray diffraction. At 122(3) GPa, a diffuse signal is observed indicating the presence of a non-crystalline phase. Structure factors have been extracted up to 182(6) GPa showing the presence of two well-defined peaks. A rapid change in the intensity ratio of the two peaks is identified between 145(10) and 151(10) GPa, indicative of a phase change. Present DFT+$U$ calculations of temperatures along Fe$_2$O$_3$ Hugoniot are in agreement with SESAME 7440 and indicate relatively low temperatures, below 2000 K, up to 150 GPa. The non-crystalline diffuse scattering is thus consistent with the - as yet unreported - shock amorphization of Fe$_2$O$_3$ between 122(3) and 145(10) GPa, followed by an amorphous-to-liquid transition above 151(10) GPa. Upon release, a non-crystalline phase is observed alongside crystalline $α$-Fe$_2$O$_3$. The extracted structure factor and pair distribution function of this release phase resemble those reported for Fe$_2$O$_3$ melt at ambient pressure. △ Less

Submitted 30 August, 2024; originally announced August 2024.

Comments: 11 pages, 4 figures, under review

Journal ref: Phys. Rev. B 111, 024209, 2025

Nanoscale Surfactant Transport: Bridging Molecular and Continuum Models

Authors: Muhammad Rizwanur Rahman, James P. Ewen, Li Shen, D. M. Heyes, Daniele Dini, E. R. Smith

Abstract: Surfactant transport is central to a diverse range of natural phenomena, and for many practical applications in physics and engineering. Surprisingly, this process remains relatively poorly understood at the molecular scale. This study investigates the mechanism behind the transport of surfactant monolayers on flat and curved liquid vapor interfaces using nonequilibrium molecular dynamics simulati… ▽ More Surfactant transport is central to a diverse range of natural phenomena, and for many practical applications in physics and engineering. Surprisingly, this process remains relatively poorly understood at the molecular scale. This study investigates the mechanism behind the transport of surfactant monolayers on flat and curved liquid vapor interfaces using nonequilibrium molecular dynamics simulations, which are compared with the continuum transport model. This approach not only provides fresh molecular level insight into surfactant dynamics, but also confirms the nanoscale mechanism of the lateral migration of surfactant molecules along a thin film that continuously deforms as surfactants spread. By connecting the continuum model where the long wave approximations prevail, to the molecular details where such approximations break down, we establish that the transport equation preserves substantial accuracy in capturing the underlying physics. Moreover, the relative importance of the different mechanisms of the transport process are identified. Consequently, we derive a novel, exact molecular equation for surfactant transport along a deforming surface. Finally, our findings demonstrate that the spreading of surfactants at the molecular scale adheres to expected scaling laws and aligns well with experimental observations. △ Less

Submitted 10 August, 2024; originally announced August 2024.

Comments: Submitted for journal publication

Journal ref: J. Fluid Mech. 1009 (2025) A18

Single Crystal Diffuse Neutron Scattering Study of the Dipole-Octupole Quantum Spin Ice Candidate Ce$_2$Zr$_2$O$_7$: No Apparent Octupolar Correlations Above $T = 0.05$ K

Authors: E. M. Smith, R. Schäfer, J. Dudemaine, B. Placke, B. Yuan, Z. Morgan, F. Ye, R. Moessner, O. Benton, A. D. Bianchi, B. D. Gaulin

Abstract: The insulating magnetic pyrochlore Ce$_2$Zr$_2$O$_7$ has gained attention as a quantum spin ice candidate with dipole-octupole character arising from the crystal electric field ground state doublet for the Ce$^{3+}$ ion. This permits both spin ice phases based on magnetic dipoles and those based on more-exotic octupoles. We report low-temperature neutron diffraction measurements on single crystal… ▽ More The insulating magnetic pyrochlore Ce$_2$Zr$_2$O$_7$ has gained attention as a quantum spin ice candidate with dipole-octupole character arising from the crystal electric field ground state doublet for the Ce$^{3+}$ ion. This permits both spin ice phases based on magnetic dipoles and those based on more-exotic octupoles. We report low-temperature neutron diffraction measurements on single crystal Ce$_2$Zr$_2$O$_7$ with $Q$-coverage both at low $Q$ where the magnetic form factor for dipoles is near maximal and at high $Q$ where the magnetic form factor for Ce$^{3+}$ octupoles is near maximal. This study was motivated by recent powder neutron diffraction studies of other Ce-based dipole-octupole pyrochlores, Ce$_2$Sn$_2$O$_7$ and Ce$_2$Hf$_2$O$_7$, which each showed temperature-dependent diffuse diffraction at high $Q$ that was interpreted as arising from octupolar correlations. Our measurements use an optimized single crystal diffuse scattering instrument that allows us to screen against strong Bragg scattering from Ce$_2$Zr$_2$O$_7$. The temperature-difference neutron diffraction reveals a low-$Q$ peak consistent with dipolar spin ice correlations reported in previous work, and an alternation between positive and negative net intensity at higher $Q$. These features are consistent with our numerical-linked-cluster calculations using pseudospin interaction parameters previously reported for Ce$_2$Zr$_2$O$_7$, Ce$_2$Sn$_2$O$_7$, and Ce$_2$Hf$_2$O$_7$. Importantly, neither the measured data nor any of the NLC calculations show evidence for increased scattering at high $Q$ resulting from octupolar correlations. We conclude that at the lowest attainable temperature for our measurements ($T = 0.05$ K), scattering from octupolar correlations in Ce$_2$Zr$_2$O$_7$ is not present in the neutron diffraction signal on the level of our observation threshold of ~ 0.1 % of the low-$Q$ dipole scattering. △ Less

Submitted 29 April, 2025; v1 submitted 10 July, 2024; originally announced July 2024.

Journal ref: Physical Review X 15, 021033 (2025)

Revealing the Electronic Structure of van der Waals Antiferromagnetic NiPS$_3$ through Synchrotron-Based $μ$-ARPES and Alkali Metal Dosing

Authors: Yifeng Cao, Qishuo Tan, Yucheng Guo, Clóvis Guerim Vieira, Mário S. C. Mazzon, Jude Laverock, Nicholas Russo, Hongze Gao, Chris Jozwiak, Aaron Bostwick, Eli Rotenberg, Jinghua Guo, Ming Yi, Matheus J. S. Matos, Xi Ling, Kevin E. Smith

Abstract: This study presents a comprehensive analysis of the band structure in NiPS$_3$, a van der Waals layered antiferromagnet, utilizing high-resolution synchrotron-based angle-resolved photoemission spectroscopy (ARPES) and corroborative density functional theory (DFT) calculations. By tuning the parameters of the light source, we obtained a very clear and wide energy range band structure of NiPS$_3$.… ▽ More This study presents a comprehensive analysis of the band structure in NiPS$_3$, a van der Waals layered antiferromagnet, utilizing high-resolution synchrotron-based angle-resolved photoemission spectroscopy (ARPES) and corroborative density functional theory (DFT) calculations. By tuning the parameters of the light source, we obtained a very clear and wide energy range band structure of NiPS$_3$. Comparison with DFT calculations allows for the identification of the orbital character of the observed bands. Our DFT calculations perfectly match the experimental results, and no adaptations were made to the calculations based on the experimental outcomes. The appearance of novel electronic structure upon alkali metal dosing (AMD) were also obtained in this ARPES study. Above valence band maximum, structure of conduction bands and bands from defect states were firstly observed in NiPS$_3$. We provide the direct determination of the band gap of NiPS$_3$ as 1.3 eV from the band structure by AMD. In addition, detailed temperature dependent ARPES spectra were obtained across a range that spans both below and above the Néel transition temperature of NiPS$_3$. We found that the paramagnetic and antiferromagnetic states have almost identical spectra, indicating the highly localized nature of Ni $d$ states. △ Less

Submitted 22 December, 2025; v1 submitted 2 July, 2024; originally announced July 2024.

Comments: 8 figures

Spectral evidence for NiPS3 as a Mott-Hubbard insulator

Authors: Yifeng Cao, Nicholas Russo, Qishuo Tan, Xi Ling, Jinghua Guo, Yi-de Chuang, Kevin E. Smith

Abstract: The layered van der Waals trichalcogenide NiPS3 has attracted widespread attention due to its unique optical, magnetic, and electronic properties. The complexity of NiPS3 itself, however, has also led to ongoing debates regarding its characteristics such as the existence of self-doped ligand holes. In this study, X-ray absorption spectroscopy and resonant inelastic X-ray scattering have been appli… ▽ More The layered van der Waals trichalcogenide NiPS3 has attracted widespread attention due to its unique optical, magnetic, and electronic properties. The complexity of NiPS3 itself, however, has also led to ongoing debates regarding its characteristics such as the existence of self-doped ligand holes. In this study, X-ray absorption spectroscopy and resonant inelastic X-ray scattering have been applied to investigate the electronic structure of NiPS3. With the aid of theoretical calculations using the charge-transfer multiplet model, we provide experimental evidence for NiPS3 being a Mott-Hubbard insulator rather than a charge-transfer insulator. Moreover, we explain why some previous XAS studies have concluded that NiPS3 is a charge-transfer insulator by comparing surface and bulk sensitive spectra. △ Less

Submitted 1 July, 2024; originally announced July 2024.

Comments: 6 figures

Thermal conversion of ultrathin nickel hydroxide for wide bandgap 2D nickel oxides

Authors: Lu Ping, Nicholas Russo, Zifan Wang, Ching-Hsiang Yao, Kevin E. Smith, Xi Ling

Abstract: Wide bandgap (WBG) semiconductors (Eg >2.0 eV) are integral to the advancement of next generation electronics, optoelectronics, and power industries, owing to their capability for high temperature operation, high breakdown voltage and efficient light emission. Enhanced power efficiency and functional performance can be attained through miniaturization, specifically via the integration of device fa… ▽ More Wide bandgap (WBG) semiconductors (Eg >2.0 eV) are integral to the advancement of next generation electronics, optoelectronics, and power industries, owing to their capability for high temperature operation, high breakdown voltage and efficient light emission. Enhanced power efficiency and functional performance can be attained through miniaturization, specifically via the integration of device fabrication into two-dimensional (2D) structure enabled by WBG 2D semiconductors. However, as an essential subgroup of WBG semiconductors, 2D transition metal oxides (TMOs) remain largely underexplored in terms of physical properties and applications in 2D opto-electronic devices, primarily due to the scarcity of sufficiently large 2D crystals. Thus, our goal is to develop synthesis pathways for 2D TMOs possessing large crystal domain (e.g. >10 nm), expanding the 2D TMOs family and providing insights for future engineering of 2D TMOs. Here, we demonstrate the synthesis of WBG 2D nickel oxide (NiO) (Eg > 2.7 eV) thermally converted from 2D nickel hydroxide (Ni(OH)2) with the lateral domain size larger than 10 um. Moreover, the conversion process is investigated using various microscopic techniques such as atomic force microscopy (AFM), Raman spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), providing significant insights on the morphology and structure variation under different oxidative conditions. The electronic structure of the converted NixOy is further investigated using multiple soft X-ray spectroscopies, such as X-ray absorption (XAS) and emission spectroscopies (XES). △ Less

Submitted 15 April, 2024; originally announced April 2024.

Phase transitions of Fe$_2$O$_3$ under laser shock compression

Authors: A. Amouretti, C. Crépisson, S. Azadi, D. Cabaret, T. Campbell, D. A. Chin, B. Colin, G. R. Collins, L. Crandall, G. Fiquet, A. Forte, T. Gawne, F. Guyot, P. Heighway, H. Lee, D. McGonegle, B. Nagler, J. Pintor, D. Polsin, G. Rousse, Y. Shi, E. Smith, J. S. Wark, S. M. Vinko, M. Harmand

Abstract: We present in-situ x-ray diffraction and velocity measurements of Fe$_2$O$_3$ under laser shock compression at pressures between 38-116 GPa. None of the phases reported by static compression studies were observed. Instead, we observed an isostructural phase transition from $α$-Fe$_2$O$_3$ to a new $α^\prime$-Fe$_2$O$_3$ phase at a pressure of 50-62 GPa. The $α^\prime$-Fe$_2$O$_3$ phase differs fro… ▽ More We present in-situ x-ray diffraction and velocity measurements of Fe$_2$O$_3$ under laser shock compression at pressures between 38-116 GPa. None of the phases reported by static compression studies were observed. Instead, we observed an isostructural phase transition from $α$-Fe$_2$O$_3$ to a new $α^\prime$-Fe$_2$O$_3$ phase at a pressure of 50-62 GPa. The $α^\prime$-Fe$_2$O$_3$ phase differs from $α$-Fe$_2$O$_3$ by an 11% volume drop and a different unit cell compressibility. We further observed a two-wave structure in the velocity profile, which can be related to an intermediate regime where both $α$ and $α^\prime$ phases coexist. Density functional theory calculations with a Hubbard parameter indicate that the observed unit cell volume drop can be associated with a spin transition following a magnetic collapse. △ Less

Submitted 28 February, 2024; originally announced February 2024.

Comments: 7 pages, 5 figures

Journal ref: Phys. Rev. Lett. 134, 176102, 2025

Resonant inelastic x-ray scattering in warm-dense Fe compounds beyond the SASE FEL resolution limit

Authors: Alessandro Forte, Thomas Gawne, Karim K. Alaa El-Din, Oliver S. Humphries, Thomas R. Preston, Céline Crépisson, Thomas Campbell, Pontus Svensson, Sam Azadi, Patrick Heighway, Yuanfeng Shi, David A. Chin, Ethan Smith, Carsten Baehtz, Victorien Bouffetier, Hauke Höppner, David McGonegle, Marion Harmand, Gilbert W. Collins, Justin S. Wark, Danae N. Polsin, Sam M. Vinko

Abstract: Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot… ▽ More Resonant inelastic x-ray scattering (RIXS) is a widely used spectroscopic technique, providing access to the electronic structure and dynamics of atoms, molecules, and solids. However, RIXS requires a narrow bandwidth x-ray probe to achieve high spectral resolution. The challenges in delivering an energetic monochromated beam from an x-ray free electron laser (XFEL) thus limit its use in few-shot experiments, including for the study of high energy density systems. Here we demonstrate that by correlating the measurements of the self-amplified spontaneous emission (SASE) spectrum of an XFEL with the RIXS signal, using a dynamic kernel deconvolution with a neural surrogate, we can achieve electronic structure resolutions substantially higher than those normally afforded by the bandwidth of the incoming x-ray beam. We further show how this technique allows us to discriminate between the valence structures of Fe and Fe$_2$O$_3$, and provides access to temperature measurements as well as M-shell binding energies estimates in warm-dense Fe compounds. △ Less

Submitted 11 January, 2024; originally announced February 2024.

TTCF4LAMMPS: A toolkit for simulation of the non-equilibrium behaviour of molecular fluids at experimentally accessible shear rates

Authors: Luca Maffioli, James P. Ewen, Edward R. Smith, Sleeba Varghese, Peter J. Daivis, Daniele Dini, B. D. Todd

Abstract: We present TTCF4LAMMPS, a toolkit for performing non-equilibrium molecular dynamics (NEMD) simulations to study fluid behaviour at low shear rates using the LAMMPS software. By combining direct NEMD simulations and the transient-time correlation function (TTCF) technique, we study the behaviour of fluids over shear rates spanning $15$ orders of magnitude. We present two example systems consisting… ▽ More We present TTCF4LAMMPS, a toolkit for performing non-equilibrium molecular dynamics (NEMD) simulations to study fluid behaviour at low shear rates using the LAMMPS software. By combining direct NEMD simulations and the transient-time correlation function (TTCF) technique, we study the behaviour of fluids over shear rates spanning $15$ orders of magnitude. We present two example systems consisting of simple monatomic systems: one containing a bulk liquid and another with a liquid layer confined between two solid walls. The small bulk system is suitable for testing on personal computers, while the larger confined system requires high-performance computing (HPC) resources. We demonstrate that the TTCF formalism can successfully detect the system response for arbitrarily weak external fields. We provide a brief mathematical explanation for this feature. Although we showcase the method for simple monatomic systems, TTCF can be readily extended to study more complex molecular fluids. Moreover, in addition to shear flows, the method can be extended to investigate elongational or mixed flows as well as thermal or electric fields. The reasonably high computational cost needed for the method is offset by the two following benefits: i) the cost is independent of the magnitude of the external field, and ii) the simulations can be made highly efficient on HPC architectures by exploiting the parallel design of LAMMPS. We expect the toolkit to be useful for computational researchers striving to study the nonequilibrium behaviour of fluids under experimentally-accessible conditions. △ Less

Submitted 27 November, 2023; originally announced December 2023.

Comments: 33 pages, 10 figures. Scripts available at the following link https://github.com/edwardsmith999/TTCF

Random Fields from Quenched Disorder in an Archetype for Correlated Electrons: the Parallel Spin Stripe Phase of La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ at the 1/8 Anomaly

Authors: Q. Chen, S. H. -Y. Huang, Q. Ma, E. M. Smith, H. Sharron, A. A. Aczel, W. Tian, B. D. Gaulin

Abstract: The parallel stripe phase is remarkable both in its own right, and in relation to the other phases it co-exists with. Its inhomogeneous nature makes such states susceptible to random fields from quenched magnetic vacancies. We argue this is the case by introducing low concentrations of nonmagnetic Zn impurities (0-10%) into La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ (Nd-LSCO) with $x$ = 0.125 in single c… ▽ More The parallel stripe phase is remarkable both in its own right, and in relation to the other phases it co-exists with. Its inhomogeneous nature makes such states susceptible to random fields from quenched magnetic vacancies. We argue this is the case by introducing low concentrations of nonmagnetic Zn impurities (0-10%) into La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ (Nd-LSCO) with $x$ = 0.125 in single crystal form, well below the percolation threshold of $\sim$ 41% for two-dimensional (2D) square lattice. Elastic neutron scattering measurements on these crystals show clear magnetic quasi-Bragg peaks at all Zn dopings. While all the Zn-doped crystals display order parameters that merge into each other and the background at $\sim$ 68 K, the temperature dependence of the order parameter as a function of Zn concentration is drastically different. This result is consistent with meandering charge stripes within the parallel stripe phase, which are pinned in the presence of quenched magnetic vacancies. In turn it implies vacancies that preferentially occupy sites within the charge stripes, and hence that can be very effective at disrupting superconductivity in Nd-LSCO ($x$ = 0.125), and, by extension, in all systems exhibiting parallel stripes. △ Less

Submitted 27 October, 2023; originally announced October 2023.

Journal ref: Phys. Rev. B 109, 134411, 2024

$μ$SR Study of the Dipole-Octupole Quantum Spin Ice Candidate Ce$_2$Zr$_2$O$_7$

Authors: J. Beare, E. M. Smith, J. Dudemaine, R. Schäfer, M. R. Rutherford, S. Sharma, A. Fitterman, C. A. Marjerrison, T. J. Williams, A. A. Aczel, S. R. Dunsiger, A. D. Bianchi, B. D. Gaulin, G. M. Luke

Abstract: The Ce$^{3+}$ pseudospin-1/2 degrees of freedom in Ce$_2$Zr$_2$O$_7$ possess both dipolar and octupolar character which enables the possibility of novel quantum spin liquid ground states in this material. Here we report new muon spin relaxation and rotation ($μ$SR) measurements on single crystal samples of Ce$_2$Zr$_2$O$_7$ in zero magnetic field and in magnetic fields directed along the… ▽ More The Ce$^{3+}$ pseudospin-1/2 degrees of freedom in Ce$_2$Zr$_2$O$_7$ possess both dipolar and octupolar character which enables the possibility of novel quantum spin liquid ground states in this material. Here we report new muon spin relaxation and rotation ($μ$SR) measurements on single crystal samples of Ce$_2$Zr$_2$O$_7$ in zero magnetic field and in magnetic fields directed along the $[1,\bar{1},0]$ and $[1,1,1]$ crystallographic directions, and for magnetic fields directed both longitudinal and transverse to the direction of muon polarization. Our zero-field results show no signs of magnetic ordering or spin freezing, consistent with earlier zero-field $μ$SR measurements on a powder sample of Ce$_2$Zr$_2$O$_7$, and also with the expectations for a quantum spin ice. However, we measure a more gentle relaxation rate for Ce$_2$Zr$_2$O$_7$ in zero-field at low temperatures than was previously reported. This difference in relaxation rate is likely due to the low oxidation, and correspondingly, the high stoichiometry of our single crystal samples. Longitudinal field measurements confirm that the magnetic dipole moments in Ce$_2$Zr$_2$O$_7$ remain dynamic at $T = 0.1$ $\mathrm{K}$. For both $[1,\bar{1},0]$ and $[1,1,1]$ magnetic fields, our $μ$SR Knight shift measurements show a field-induced leveling off of the magnetic susceptibility at low temperature which is qualitatively consistent with corresponding calculations using the numerical-linked-cluster method in combination with recent estimates for the nearest-neighbour exchange parameters of Ce$_2$Zr$_2$O$_7$. △ Less

Submitted 7 November, 2023; v1 submitted 5 August, 2023; originally announced August 2023.

Journal ref: Physical Review B 108, 174411 (2023)

Quantum Spin Ice Response to a Magnetic Field in the Dipole-Octupole Pyrochlore Ce$_2$Zr$_2$O$_7$

Authors: E. M. Smith, J. Dudemaine, B. Placke, R. Schäfer, D. R. Yahne, T. DeLazzer, A. Fitterman, J. Beare, J. Gaudet, C. R. C. Buhariwalla, A. Podlesnyak, Guangyong Xu, J. P. Clancy, R. Movshovich, G. M. Luke, K. A. Ross, R. Moessner, O. Benton, A. D. Bianchi, B. D. Gaulin

Abstract: We report new heat capacity measurements on single crystal Ce$_2$Zr$_2$O$_7$ down to $\sim$ 0.1 K in a magnetic field along the $[1,\bar{1}, 0]$ direction. These new measurements show that the broad hump in the zero-field heat capacity moves higher in temperature with increasing field strength and is split into two humps by the $[1,\bar{1}, 0]$ field at $\sim$ 2 T. These separate features are due… ▽ More We report new heat capacity measurements on single crystal Ce$_2$Zr$_2$O$_7$ down to $\sim$ 0.1 K in a magnetic field along the $[1,\bar{1}, 0]$ direction. These new measurements show that the broad hump in the zero-field heat capacity moves higher in temperature with increasing field strength and is split into two humps by the $[1,\bar{1}, 0]$ field at $\sim$ 2 T. These separate features are due to the decomposition of the pyrochlore lattice into effectively decoupled chains for fields in this direction: one set of chains ($α$-chains) is polarized by the field while the other ($β$-chains) remains free. Our theoretical modelling suggests that the $β$-chains are close to a critical state, with nearly-gapless excitations. We also report new elastic and inelastic neutron scattering measurements on single crystal Ce$_2$Zr$_2$O$_7$ in $[1, \bar{1}, 0]$ and $[0, 0, 1]$ magnetic fields at temperatures down to 0.03 K. The elastic scattering behaves consistently with the formation of independent chains for a $[1, \bar{1}, 0]$ field, while the $[0, 0, 1]$ field produces a single field-induced magnetic Bragg peak at $(0, 2, 0)$ and equivalent wavevectors, indicating a polarized spin ice for fields above $\sim$ 3 T. For both $[1, \bar{1}, 0]$ and $[0, 0, 1]$ fields, our inelastic neutron scattering results show an approximately-dispersionless continuum of scattering that increases in both energy and intensity with increasing field strength. By modelling the complete set of experimental data using numerical linked cluster and semiclassical molecular dynamics calculations, we demonstrate the dominantly multipolar nature of the exchange interactions in Ce$_2$Zr$_2$O$_7$ and the smallness of the parameter $θ$ which controls the mixing between dipolar and octupolar degrees of freedom. These results support previous estimates of the microscopic exchange parameters. △ Less

Submitted 29 August, 2023; v1 submitted 22 June, 2023; originally announced June 2023.

Journal ref: Physical Review B 108, 054438 (2023)

14 Examples of How LLMs Can Transform Materials Science and Chemistry: A Reflection on a Large Language Model Hackathon

Authors: Kevin Maik Jablonka, Qianxiang Ai, Alexander Al-Feghali, Shruti Badhwar, Joshua D. Bocarsly, Andres M Bran, Stefan Bringuier, L. Catherine Brinson, Kamal Choudhary, Defne Circi, Sam Cox, Wibe A. de Jong, Matthew L. Evans, Nicolas Gastellu, Jerome Genzling, María Victoria Gil, Ankur K. Gupta, Zhi Hong, Alishba Imran, Sabine Kruschwitz, Anne Labarre, Jakub Lála, Tao Liu, Steven Ma, Sauradeep Majumdar , et al. (28 additional authors not shown)

Abstract: Large-language models (LLMs) such as GPT-4 caught the interest of many scientists. Recent studies suggested that these models could be useful in chemistry and materials science. To explore these possibilities, we organized a hackathon. This article chronicles the projects built as part of this hackathon. Participants employed LLMs for various applications, including predicting properties of mole… ▽ More Large-language models (LLMs) such as GPT-4 caught the interest of many scientists. Recent studies suggested that these models could be useful in chemistry and materials science. To explore these possibilities, we organized a hackathon. This article chronicles the projects built as part of this hackathon. Participants employed LLMs for various applications, including predicting properties of molecules and materials, designing novel interfaces for tools, extracting knowledge from unstructured data, and developing new educational applications. The diverse topics and the fact that working prototypes could be generated in less than two days highlight that LLMs will profoundly impact the future of our fields. The rich collection of ideas and projects also indicates that the applications of LLMs are not limited to materials science and chemistry but offer potential benefits to a wide range of scientific disciplines. △ Less

Submitted 14 July, 2023; v1 submitted 9 June, 2023; originally announced June 2023.

Spin-orbital order and excitons in magnetoresistive HoBi

Authors: J. Gaudet, H. -Y. Yang, E. M. Smith, T. Halloran, J. P. Clancy, J. A. Rodriguez-Rivera, Guangyong Xu, Y. Zhao, W. C. Chen, G. Sala, A. A. Aczel, B. D. Gaulin, F. Tafti, C. Broholm

Abstract: The magnetism of the rock-salt $fcc$ rare-earth monopnictide HoBi, a candidate topological material with extreme magnetoresistance, is investigated. From the Ho$^{3+}$ non-Kramers $J$=8 spin-orbital multiplet, the cubic crystal electric field yields six nearly degenerate low-energy levels. These constitute an anisotropic magnetic moment with a Jahn-Teller-like coupling to the lattice. In the cubic… ▽ More The magnetism of the rock-salt $fcc$ rare-earth monopnictide HoBi, a candidate topological material with extreme magnetoresistance, is investigated. From the Ho$^{3+}$ non-Kramers $J$=8 spin-orbital multiplet, the cubic crystal electric field yields six nearly degenerate low-energy levels. These constitute an anisotropic magnetic moment with a Jahn-Teller-like coupling to the lattice. In the cubic phase for $T>T_N~=~5.72(1)~K$, the paramagnetic neutron scattering is centered at $\mathbf{k}=(\frac{1}{2}\frac{1}{2}\frac{1}{2})$ and was fit to dominant antiferromagnetic interactions between Ho spins separated by $\{100\}$ and ferromagnetic interactions between spins displaced by $\{\frac{1}{2}\frac{1}{2}0\}$. For $T<T_N$, a type-II AFM long-range order with $\mathbf{k}=(\frac{1}{2}\frac{1}{2}\frac{1}{2})$ develops along with a tetragonal lattice distortion. While neutron diffraction from a multi-domain sample cannot unambiguously determine the spin orientation within a domain, the bulk magnetization, structural distortion, and our measurements of the magnetic excitations all show the easy axis coincides with the tetragonal axis. The weakly dispersive excitons for $T<T_N$ can be accounted for by a spin Hamiltonian that includes the crystal electric field and exchange interactions within the Random Phase Approximation. △ Less

Submitted 12 January, 2023; originally announced January 2023.

Comments: 10 pages, 6 figures

Observation of suppressed viscosity in the normal state of $^3$He due to superfluid fluctuations

Authors: Rakin N. Baten, Yefan Tian, Eric N. Smith, Erich Mueller, Jeevak M. Parpia

Abstract: By monitoring the quality factor of a quartz tuning fork oscillator we have observed a fluctuation-driven reduction in the viscosity of bulk $^3$He in the normal state near the superfluid transition temperature, $T_c$. These fluctuations, which are only found within $100 μ$K of $T_c$, play a vital role in the theoretical modeling of ordering; they encode details about the Fermi liquid parameters,… ▽ More By monitoring the quality factor of a quartz tuning fork oscillator we have observed a fluctuation-driven reduction in the viscosity of bulk $^3$He in the normal state near the superfluid transition temperature, $T_c$. These fluctuations, which are only found within $100 μ$K of $T_c$, play a vital role in the theoretical modeling of ordering; they encode details about the Fermi liquid parameters, pairing symmetry, and scattering phase shifts. They will be of crucial importance for transport probes of the topologically nontrivial features of superfluid $^3$He under strong confinement. Here we characterize the temperature and pressure dependence of the fluctuation signature, finding data collapse consistent with the predicted theoretical behavior. △ Less

Submitted 25 August, 2023; v1 submitted 23 December, 2022; originally announced December 2022.

Comments: 5 figures

Dipolar spin ice regime proximate to an all-in-all-out Néel ground state in the dipolar-octupolar pyrochlore Ce$_2$Sn$_2$O$_7$

Authors: D. R. Yahne, B. Placke, R. Schäfer, O. Benton, R. Moessner, M. Powell, J. W. Kolis, C. M. Pasco, A. F. May, M. D. Frontzek, E. M. Smith, B. D. Gaulin, S. Calder, K. A. Ross

Abstract: The dipolar-octupolar (DO) pyrochlores, R$_2$M$_2$O$_7$ (R = Ce, Sm, Nd), are key players in the search for realizable novel quantum spin liquid (QSL) states as a large parameter space within the DO pyrochlore phase diagram is theorized to host QSL states of both dipolar and octupolar nature. New single crystals and powders of Ce$_2$Sn$_2$O$_7$, synthesized by hydrothermal techniques, present an o… ▽ More The dipolar-octupolar (DO) pyrochlores, R$_2$M$_2$O$_7$ (R = Ce, Sm, Nd), are key players in the search for realizable novel quantum spin liquid (QSL) states as a large parameter space within the DO pyrochlore phase diagram is theorized to host QSL states of both dipolar and octupolar nature. New single crystals and powders of Ce$_2$Sn$_2$O$_7$, synthesized by hydrothermal techniques, present an opportunity for a new characterization of the exchange parameters in Ce$_2$Sn$_2$O$_7$ using the near-neighbor $XYZ$ model Hamiltonian associated with DO pyrochlores. Utilizing quantum numerical linked cluster expansion fits to heat capacity and magnetic susceptibility measurements, and classical Monte Carlo calculations to the diffuse neutron diffraction of the new hydrothermally grown Ce$_2$Sn$_2$O$_7$ samples, we place Ce$_2$Sn$_2$O$_7$'s ground state within the ordered dipolar all-in-all-out (AIAO) Néel phase, with quantum Monte Carlo calculations showing a transition to long-range order at temperatures below those accessed experimentally. Indeed, our new neutron diffraction measurements on the hydrothermally grown Ce$_2$Sn$_2$O$_7$ powders show a broad signal at low scattering wave vectors, reminiscent of a \textit{dipolar} spin ice, in striking contrast from previous powder neutron diffraction on samples grown from solid-state synthesis, which found diffuse scattering at high scattering wave vectors associated with magnetic {\it octupoles} and suggested an octupolar quantum spin ice state. We conclude that new hydrothermally grown Ce$_2$Sn$_2$O$_7$ samples host a finite-temperature proximate dipolar spin ice phase, above the expected transition to AIAO Néel order. △ Less

Submitted 26 January, 2024; v1 submitted 28 November, 2022; originally announced November 2022.

Comments: 16 pages, 12 figures

Journal ref: D. R. Yahne et al., Phys. Rev. X 14, 011005 (2024)

Action Functional Gradient Descent algorithm for estimating escape paths in Stochastic Chemical Reaction Networks

Authors: Praful Gagrani, Eric Smith

Abstract: We first derive the Hamilton-Jacobi theory underlying continuous-time Markov processes, and then use the construction to develop a variational algorithm for estimating escape (least improbable or first passage) paths for a generic stochastic chemical reaction network that exhibits multiple fixed points. The design of our algorithm is such that it is independent of the underlying dimensionality of… ▽ More We first derive the Hamilton-Jacobi theory underlying continuous-time Markov processes, and then use the construction to develop a variational algorithm for estimating escape (least improbable or first passage) paths for a generic stochastic chemical reaction network that exhibits multiple fixed points. The design of our algorithm is such that it is independent of the underlying dimensionality of the system, the discretization control parameters are updated towards the continuum limit, and there is an easy-to-calculate measure for the correctness of its solution. We consider several applications of the algorithm and verify them against computationally expensive means such as the shooting method and stochastic simulation. While we employ theoretical techniques from mathematical physics, numerical optimization and chemical reaction network theory, we hope that our work finds practical applications with an inter-disciplinary audience including chemists, biologists, optimal control theorists and game theorists. △ Less

Submitted 6 February, 2023; v1 submitted 24 October, 2022; originally announced October 2022.

Comments: 40 pages, 21 figures

A perspective on the microscopic pressure (stress) tensor: history, current understanding, and future challenges

Authors: Kaihang Shi, Edward Smith, Erik E. Santiso, Keith E. Gubbins

Abstract: The pressure tensor (equivalent to the negative stress tensor) at both microscopic and macroscopic levels is fundamental to many aspects of engineering and science, including fluid dynamics, solid mechanics, biophysics, and thermodynamics. In this perspective paper, we review methods to calculate the microscopic pressure tensor. Connections between different pressure forms for equilibrium and non-… ▽ More The pressure tensor (equivalent to the negative stress tensor) at both microscopic and macroscopic levels is fundamental to many aspects of engineering and science, including fluid dynamics, solid mechanics, biophysics, and thermodynamics. In this perspective paper, we review methods to calculate the microscopic pressure tensor. Connections between different pressure forms for equilibrium and non-equilibrium systems are established. We also point out several challenges in the field, including the historical controversies over the definition of the microscopic pressure tensor; the difficulties with many-body and long-range potentials; the insufficiency of software and computational tools; and the lack of experimental routes to probe the pressure tensor at the nanoscale. Possible future directions are suggested. △ Less

Submitted 19 January, 2023; v1 submitted 3 October, 2022; originally announced October 2022.

Comments: This is the final version accepted by The Journal of Chemical Physics (in press). The link to the article is https://aip.scitation.org/doi/abs/10.1063/5.0132487

Journal ref: The Journal of Chemical Physics (2022)

Reply to "Comment on: 'Case for a U(1)$_π$ Quantum Spin Liquid Ground State in the Dipole-Octupole Pyrochlore $\mathrm{Ce}_2\mathrm{Zr}_2\mathrm{O}_7$' "

Authors: E. M. Smith, O. Benton, D. R. Yahne, B. Placke, R. Schäfer, J. Gaudet, J. Dudemaine, A. Fitterman, J. Beare, A. R. Wildes, S. Bhattacharya, T. DeLazzer, C. R. C. Buhariwalla, N. P. Butch, R. Movshovich, J. D. Garrett, C. A. Marjerrison, J. P. Clancy, E. Kermarrec, G. M. Luke, A. D. Bianchi, K. A. Ross, B. D. Gaulin

Abstract: In his comment [arXiv:2209.03235], S. W. Lovesey argues that our analysis of neutron scattering experiments performed on Ce$_2$Zr$_2$O$_7$ is invalid. Lovesey argues that we have not properly accounted for the higher-order multipolar contributions to the magnetic scattering and that our use of pseudospin-$1/2$ operators to describe the scattering is inappropriate. In this reply, we show that the m… ▽ More In his comment [arXiv:2209.03235], S. W. Lovesey argues that our analysis of neutron scattering experiments performed on Ce$_2$Zr$_2$O$_7$ is invalid. Lovesey argues that we have not properly accounted for the higher-order multipolar contributions to the magnetic scattering and that our use of pseudospin-$1/2$ operators to describe the scattering is inappropriate. In this reply, we show that the multipolar corrections discussed by Lovesey only become significant at scattering wavevectors exceeding those accessed in our experiments. This in no way contradicts or undermines our work, which never claimed a direct observation of scattering from higher-order multipoles. We further show that Lovesey's objections to our use of pseudospins are unfounded, and that the pseudospin operators are able to describe all magnetic scattering processes at the energy scale of our experiments, far below the crystal field gap. Finally, we comment on certain assumptions in Lovesey's calculations of the scattering amplitude which are inconsistent with experiment. △ Less

Submitted 30 September, 2022; v1 submitted 29 September, 2022; originally announced September 2022.

Comments: 6 pages, 1 figure

Supercooling of the A phase of $^3$He

Authors: Yefan Tian, Dmytro Lotnyk, Anna Eyal, Kuang Zhang, Nikolay Zhelev, T. S. Abhilash, Aldo Chavez, Eric Smith, Mark Hindmarsh, John Saunders, Erich Mueller, Jeevak Parpia

Abstract: Because of the extreme purity, lack of disorder, and complex order parameter, the first-order superfluid $^3$He A-B transition is the leading model system for first order transitions in the early universe. Here we report on the path dependence of the supercooling of the A phase over a wide range of pressures below 29.3 bar at nearly zero magnetic field. The A phase can be cooled significantly belo… ▽ More Because of the extreme purity, lack of disorder, and complex order parameter, the first-order superfluid $^3$He A-B transition is the leading model system for first order transitions in the early universe. Here we report on the path dependence of the supercooling of the A phase over a wide range of pressures below 29.3 bar at nearly zero magnetic field. The A phase can be cooled significantly below the thermodynamic A-B transition temperature. While the extent of supercooling is highly reproducible, it depends strongly upon the cooling trajectory: The metastability of the A phase is enhanced by transiting through regions where the A phase is more stable. We provide evidence that some of the additional supercooling is due to the elimination of B phase seeds formed upon passage through the superfluid transition. A greater understanding of the physics is essential before the $^3$He can be exploited to model transitions in the early universe. △ Less

Submitted 25 August, 2022; originally announced August 2022.

Comments: 6 Figures

Magnetic Field Tuning of Parallel Spin Stripe Order and Fluctuations near the Pseudogap Quantum Critical Point in La$_{1.36}$Nd$_{0.4}$Sr$_{0.24}$CuO$_4$

Authors: Qianli Ma, Evan M. Smith, Zachary W. Cronkwright, Mirela Dragomir, Gabrielle Mitchell, Barry W. Winn, Travis J. Williams, Bruce D. Gaulin

Abstract: A quantum critical point in the single layer, hole-doped cuprate system La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ (Nd-LSCO), near $x$ = 0.23 has been proposed as an organizing principle for understanding high temperature superconductivity. Our earlier neutron diffraction work on Nd-LSCO at optimal and high doping revealed static parallel spin stripes to exist out to the QCP and slightly beyond, at $x$ =… ▽ More A quantum critical point in the single layer, hole-doped cuprate system La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ (Nd-LSCO), near $x$ = 0.23 has been proposed as an organizing principle for understanding high temperature superconductivity. Our earlier neutron diffraction work on Nd-LSCO at optimal and high doping revealed static parallel spin stripes to exist out to the QCP and slightly beyond, at $x$ = 0.24 and 0.26. We examine more closely the parallel spin stripe order parameter in Nd-LSCO in both zero magnetic field and fields up to 8 T for H // c in these single crystals. In contrast to earlier studies at lower doping, we observe that H //c in excess of $\sim$ 2.5 T eliminates the incommensurate quasi-Bragg peaks associated with parallel spin stripes. But this elastic scattering is not destroyed by the field; rather it is transferred to commensurate {\textbf{Q} = 0} Bragg positions, implying that the spins participating in the spin stripes have been polarized. Inelastic neutron scattering measurements at high fields show an increase in the low energy, parallel spin stripe fluctuations and evidence for a spin gap, $Δ_{spin}$= 3 $\pm$ 0.5 meV for Nd-LSCO with $x$ = 0.24. This is shown to be consistent with spin gap measurements as a function of superconducting T$_C$ over five different families of cuprate superconductors, which follow the approximate linear relation, $Δ_{spin}$ = 3.5 k$_B$T$_C$. △ Less

Submitted 21 April, 2022; v1 submitted 20 April, 2022; originally announced April 2022.

Slip and Stress From Low Strain-Rate Nonequilibrium Molecular Dynamics: The Transient-Time Correlation Function Technique

Authors: Luca Maffioli, Edward R. Smith, James P. Ewen, Peter J. Daivis, Daniele Dini, B. D. Todd

Abstract: We derive the transient-time correlation function (TTCF) expression for the computation of phase variables of inhomogenous confined atomistic fluids undergoing boundary-driven planar shear (Couette) flow at constant pressure. Using nonequilibrium molecular dynamics simulations, we then apply the TTCF formalism to the computation of the shear stress and the slip velocity for atomistic fluids at rea… ▽ More We derive the transient-time correlation function (TTCF) expression for the computation of phase variables of inhomogenous confined atomistic fluids undergoing boundary-driven planar shear (Couette) flow at constant pressure. Using nonequilibrium molecular dynamics simulations, we then apply the TTCF formalism to the computation of the shear stress and the slip velocity for atomistic fluids at realistic low shear rates, in systems under constant pressure and constant volume. We show that, compared to direct averaging of multiple trajectories, the TTCF method dramatically improves the accuracy of the results at low shear rates, and that it is suitable to investigate the tribology and rheology of atomistically detailed confined fluids at realistic flow rates. △ Less

Submitted 16 February, 2022; originally announced February 2022.

Journal ref: J. Chem. Phys. 156, 184111 (2022)

Full Configuration Interaction Excited-State Energies in Large Active Spaces from Subspace Iteration with Repeated Random Sparsification

Authors: Samuel M. Greene, Robert J. Webber, James E. T. Smith, Jonathan Weare, Timothy C. Berkelbach

Abstract: We present a stable and systematically improvable quantum Monte Carlo (QMC) approach to calculating excited-state energies, which we implement using our fast randomized iteration method for the full configuration interaction problem (FCI-FRI). Unlike previous excited-state quantum Monte Carlo methods, our approach, which is an asymmetric variant of subspace iteration, avoids the use of dot product… ▽ More We present a stable and systematically improvable quantum Monte Carlo (QMC) approach to calculating excited-state energies, which we implement using our fast randomized iteration method for the full configuration interaction problem (FCI-FRI). Unlike previous excited-state quantum Monte Carlo methods, our approach, which is an asymmetric variant of subspace iteration, avoids the use of dot products of random vectors and instead relies upon trial vectors to maintain orthogonality and estimate eigenvalues. By leveraging recent advances, we apply our method to calculate ground- and excited-state energies of strongly correlated molecular systems in large active spaces, including the carbon dimer with 8 electrons in 108 orbitals (8e,108o), an oxo-Mn(salen) transition metal complex (28e,28o), ozone (18e,87o), and butadiene (22e,82o). In the majority of these test cases, our approach yields total excited-state energies that agree with those from state-of-the-art methods -- including heat-bath CI, the density matrix renormalization group approach, and FCIQMC -- to within sub-milliHartree accuracy. In all cases, estimated excitation energies agree to within about 0.1 eV. △ Less

Submitted 12 October, 2022; v1 submitted 28 January, 2022; originally announced January 2022.

Comments: 16 pages, 5 figures, 3 tables

Skyrmion Alignment and Pinning Effects in a Disordered Multi-Phase Skyrmion Material Co8Zn8Mn4

Authors: M. E. Henderson, M. Bleuel, J. Beare, D. G. Cory, B. Heacock, M. G. Huber, G. M. Luke, M. Pula, D. Sarenac, S. Sharma, E. M. Smith, K. Zhernenkov, D. A. Pushin

Abstract: Underlying disorder in skyrmion materials may both inhibit and facilitate skyrmion reorientations and changes in topology. The identification of these disorder-induced topologically active regimes is critical to realizing robust skyrmion spintronic implementations, yet few studies exist for disordered bulk samples. Here, we employ small-angle neutron scattering (SANS) and micromagnetic simulations… ▽ More Underlying disorder in skyrmion materials may both inhibit and facilitate skyrmion reorientations and changes in topology. The identification of these disorder-induced topologically active regimes is critical to realizing robust skyrmion spintronic implementations, yet few studies exist for disordered bulk samples. Here, we employ small-angle neutron scattering (SANS) and micromagnetic simulations to examine the influence of skyrmion order on skyrmion lattice formation, transition, and reorientation dynamics across the phase space of a disordered polycrystalline Co$_{8}$Zn$_{8}$Mn$_{4}$ bulk sample. Our measurements reveal a new disordered-to-ordered skyrmion square lattice transition pathway characterized by the novel promotion of four-fold order in SANS and accompanied by a change in topology of the system, reinforced through micromagnetic simulations. Pinning responses are observed to dominate skyrmion dynamics in the metastable triangular lattice phase, enhancing skyrmion stabilization through a remarkable and previously undetected skyrmion memory effect which reproduces previous ordering processes and persists in zero field. These results uncover the cooperative interplay of anisotropy and disorder in skyrmion formation and restructuring dynamics, establishing new tunable pathways for skyrmion manipulation. △ Less

Submitted 17 August, 2022; v1 submitted 16 December, 2021; originally announced December 2021.

Comments: 15 pages, 11 figures, Version 2 showing micromagnetic simulations that reinforce a new disordered-to-ordered square lattice skyrmion transition pathway which entails a change in topological charge. SANS simulations are included which estimate the change in the skyrmion lattice and ferromagnetic volume fractions from the metastable triangular lattice skyrmion phase to the skyrmion memory phase

Chiral Phase Change Nanomaterials

Authors: Joshua A. Burrow, Md Shah Alam, Evan M. Smith, Riad Yahiaoui, Ryan Laing, Piyush J. Shah, Thomas A. Searles, Shivashankar Vangala, Joshua R. Hendrickson, Andrew Sarangan, Imad Agha

Abstract: Chiral nanostructures offer the ability to respond to the vector nature of a light beam at the nanoscale. While naturally chiral materials offer a path towards scalability, engineered structures offer a path to wavelength tunability through geometric manipulation. Neither approach, however, allows for temporal control of chirality. Therefore, in the best of all worlds, it is crucial to realize chi… ▽ More Chiral nanostructures offer the ability to respond to the vector nature of a light beam at the nanoscale. While naturally chiral materials offer a path towards scalability, engineered structures offer a path to wavelength tunability through geometric manipulation. Neither approach, however, allows for temporal control of chirality. Therefore, in the best of all worlds, it is crucial to realize chiral materials that possess the quality of scalability, tailored wavelength response, and dynamic control at high speeds. Here, a new class of intrinsically chiral phase change nanomaterials (PCNMs) is proposed and explored, based on a scalable bottom-up fabrication technique with a high degree of control in three dimensions. Angular resolved Mueller Matrix and spectroscopic ellipsometry are performed to characterize the optical birefringence and dichroism, and a numerical model is provided to explain the origin of optical activity. This work achieves the critical goal of demonstrating high-speed dynamic switching of chirality over 50,000 cycles via the underlying PCNM. △ Less

Submitted 18 November, 2021; originally announced November 2021.

Comments: 21 pages, 10 page supplement, 16 figures

Multiscale Mechanical Consequences of Ocean Acidification for Cold-Water Corals

Authors: Uwe Wolfram, Marta Peña-Fernandez, Samuel McPhee, Ewan Smith, Rainer J. Beck, Jonathan D. Shephard, Ali Ozel, Craig Scott Erskine, Janina Büscher, Jürgen Titschack, J. Murray Roberts, Sebastian Hennige

Abstract: Ocean acidification is a threat to deep-sea corals and could lead to dramatic and rapid loss of the reef framework habitat they build. Weakening of structurally critical parts of the coral reef framework can lead to physical habitat collapse on an ecosystem scale, reducing the potential for biodiversity support. The mechanism underpinning crumbling and collapse of corals can be described via a com… ▽ More Ocean acidification is a threat to deep-sea corals and could lead to dramatic and rapid loss of the reef framework habitat they build. Weakening of structurally critical parts of the coral reef framework can lead to physical habitat collapse on an ecosystem scale, reducing the potential for biodiversity support. The mechanism underpinning crumbling and collapse of corals can be described via a combination of laboratory-scale experiments and mathematical and computational models. We synthesise data from electron back-scatter diffraction, micro-computed tomography, and micromechanical experiments, supplemented by molecular dynamics and continuum micromechanics simulations to predict failure of coral structures under increasing porosity and dissolution. Results reveal remarkable mechanical properties of cold-water coral skeletons of 462 MPa compressive strength and 45-67 GPa stiffness. This is 10 times stronger than concrete, twice as strong than ultrahigh performance fibre reinforced concrete, or nacre. Contrary to what would be expected, CWCs skeletons retain their strength despite a loss of stiffness and even when synthesised under future oceanic conditions. Our models capture the impact of corrosive waters on exposed skeletons and illustrate how small modifications in their skeleton lead to significantly increased risk of crumbling coral habitat. This new understanding, combined with projections of how seawater chemistry will change over the coming decades, will help support future conservation and management efforts of these vulnerable marine ecosystems by identifying which ecosystems are at risk and when they will be at risk, allowing assessment of the impact upon associated biodiversity. △ Less

Submitted 2 May, 2022; v1 submitted 4 October, 2021; originally announced October 2021.

Comments: 45 (article + supplements), 8 Figures, 2 Tables

Dynamic Parallel Spin Stripes from the 1/8 anomaly to the End of Superconductivity in La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$

Authors: Qianli Ma, Evan M. Smith, Zachary W. Cronkwright, Mirela Dragomir, Gabrielle Mitchell, Alexander I. Kolesnikov, Matthew B. Stone, Bruce D. Gaulin

Abstract: We have carried out new neutron spectroscopic measurements on single crystals of La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ from 0.12 to 0.26 using time-of-flight techniques. These measurements allow us to follow the evolution of parallel spin stripe fluctuations with energies less than 33 meV, from x=0.12 to 0.26. Samples at these hole-doping levels are known to display static (on the neutron scattering… ▽ More We have carried out new neutron spectroscopic measurements on single crystals of La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ from 0.12 to 0.26 using time-of-flight techniques. These measurements allow us to follow the evolution of parallel spin stripe fluctuations with energies less than 33 meV, from x=0.12 to 0.26. Samples at these hole-doping levels are known to display static (on the neutron scattering time scale) parallel spin stripes at low temperature, with onset temperatures and intensities which decrease rapidly with increasing x. Nonetheless, we report remarkably similar dynamic spectral weight for the corresponding dynamic parallel spin stripes, between 5 meV to 33 meV, from the 1/8 anomaly near x=0.12, to optimal doping near x=0.19 to the quantum critical point for the pseudogap phase near x=0.24, and finally to the approximate end of superconductivity near x=0.26. This observed dynamic magnetic spectral weight is structured in energy with a peak near 17 meV at all dopings studied. Earlier neutron and resonant x-ray scattering measurements on related cuprate superconductors have reported both a disappearance with increasing doping of magnetic fluctuations at ($π$, $π$) wavevectors characterizing parallel spin stripe structures, and persistant paramagnon scattering away from this wavevector, respectively. Our new results on La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ from 0.12 < x <0.26 clearly show persistent parallel spin stripe fluctuations at and around at ($π$, $π$), and across the full range of doping studied. These results are also compared to recent theory. Together with a rapidly declining x-dependence to the static parallel spin stripe order, the persistent parallel spin stripe fluctuations show a remarkable similarity to the expectations of a quantum spin glass, random t-J model, recently introduced to describe strong local correlations in cuprates. △ Less

Submitted 25 January, 2022; v1 submitted 23 September, 2021; originally announced September 2021.

Nonequilibrium Time Reversibility with Maps and Walks

Authors: William Graham Hoover, Carol Griswold Hoover, Edward R. Smith

Abstract: Time-reversible dynamical simulations of nonequilibrium systems exemplify both Loschmidt's and Zermélo's paradoxes. That is, computational time-reversible simulations invariably produce solutions consistent with the {\it irreversible} Second Law of Thermodynamics (Loschmidt's) as well as {\it periodic} in the time (Zermélo's, illustrating Poincaré recurrence). Understanding these paradoxical aspec… ▽ More Time-reversible dynamical simulations of nonequilibrium systems exemplify both Loschmidt's and Zermélo's paradoxes. That is, computational time-reversible simulations invariably produce solutions consistent with the {\it irreversible} Second Law of Thermodynamics (Loschmidt's) as well as {\it periodic} in the time (Zermélo's, illustrating Poincaré recurrence). Understanding these paradoxical aspects of time-reversible systems is enhanced here by studying the simplest pair of such model systems. The first is time-reversible, but nevertheless dissipative and periodic, the piecewise-linear compressible Baker Map. The fractal properties of that two-dimensional map are mirrored by an even simpler example, the one-dimensional random walk, confined to the unit interval. As a further puzzle the two models yield ambiguities in determining the fractals' information dimensions. These puzzles, including the classical paradoxes, are reviewed and explored here. We review our investigations presented in Budapest in 1997 and end with presentday questions posed as the Snook Prize Problems in 2020 and 2021. △ Less

Submitted 19 September, 2021; v1 submitted 4 August, 2021; originally announced August 2021.

Comments: Eighteen pages with 11 Figures

The case for a U(1)$_π$ Quantum Spin Liquid Ground State in the Dipole-Octupole Pyrochlore Ce$_2$Zr$_2$O$_7$

Authors: E. M. Smith, O. Benton, D. R. Yahne, B. Placke, R. Schäfer, J. Gaudet, J. Dudemaine, A. Fitterman, J. Beare, A. R. Wildes, S. Bhattacharya, T. DeLazzer, C. R. C. Buhariwalla, N. P. Butch, R. Movshovich, J. D. Garrett, C. A. Marjerrison, J. P. Clancy, E. Kermarrec, G. M. Luke, A. D. Bianchi, K. A. Ross, B. D. Gaulin

Abstract: The Ce$^{3+}$ pseudospin-$\frac{1}{2}$ degrees of freedom in the pyrochlore magnet Ce$_2$Zr$_2$O$_7$ are known to possess dipole-octupole (DO) character, making it a candidate for novel quantum spin liquid (QSL) ground states at low temperatures. We report new polarized neutron diffraction at low temperatures, as well as heat capacity ($C_p$) measurements on single crystal Ce$_2$Zr$_2$O$_7$. The f… ▽ More The Ce$^{3+}$ pseudospin-$\frac{1}{2}$ degrees of freedom in the pyrochlore magnet Ce$_2$Zr$_2$O$_7$ are known to possess dipole-octupole (DO) character, making it a candidate for novel quantum spin liquid (QSL) ground states at low temperatures. We report new polarized neutron diffraction at low temperatures, as well as heat capacity ($C_p$) measurements on single crystal Ce$_2$Zr$_2$O$_7$. The former bears both similarities and differences from that measured in the canonical dipolar spin ice compound Ho$_2$Ti$_2$O$_7$, while the latter rises sharply at low temperatures, initially plateauing near 0.08 K, before falling off towards a high temperature zero beyond 3 K. Above $\sim$0.5 K, the $C_p$ data set can be fit to the results of a quantum numerical linked cluster (NLC) calculation, carried out to 4$^{\mathrm{th}}$ order, that allows estimates for the terms in the near-neighbour XYZ Hamiltonian expected for such DO pyrochlore systems. Fits of the same theory to the temperature dependence of the magnetic susceptibility and unpolarized neutron scattering complement this analysis. A comparison between the resulting best fit NLC calculation and the polarized neutron diffraction shows both agreement and discrepancies, mostly in the form of zone-boundary diffuse scattering in the non-spin flip channel, which are attributed to interactions beyond near-neighbours. The lack of an observed thermodynamic anomaly and the constraints on the near-neighbour XYZ Hamiltonian suggest that Ce$_2$Zr$_2$O$_7$ realizes a U(1)$_π$ QSL state at low temperatures, and one that likely resides near the boundary between dipolar and octupolar character. △ Less

Submitted 8 December, 2021; v1 submitted 2 August, 2021; originally announced August 2021.

Comments: 11 pages, 11 figures

Journal ref: Physical Review X 12, 021015 (2022)

The Importance of Reference Frame for Pressure at the Liquid-Vapour Interface

Authors: Edward R. Smith

Abstract: The local pressure tensor is non-unique, a fact which has generated confusion and debate in the seventy years since the seminal work by Irving Kirkwood. This non-uniqueness is normally attributed to the interaction path between molecules, especially in the interfacial-science community. In this work we reframe this discussion of non-uniqueness in terms of the location, or reference frame, used to… ▽ More The local pressure tensor is non-unique, a fact which has generated confusion and debate in the seventy years since the seminal work by Irving Kirkwood. This non-uniqueness is normally attributed to the interaction path between molecules, especially in the interfacial-science community. In this work we reframe this discussion of non-uniqueness in terms of the location, or reference frame, used to measure the pressure. By using a general mathematical description of the liquid-vapour interface, we obtain a reference frame that moves with the interface through time, providing a new insight into the pressure. We compare this instantaneous moving reference frame with the fixed Eulerian one. Through this process, we show the requirement that normal pressure balance at the moving surface is satisfied by surface fluxes, however an additional corrective term based on surface curvature is required for the average pressure in a volume. We make the case that a focus on the path of integration is the cause of much of the confusion in the literature. Using an explicit reference frame with a more general derivation of pressure clarifies some of the issues of uniqueness in the pressure tensor and provides a pressure tensor which is defined at any instant in time and valid away from thermodynamic equilibrium. △ Less

Submitted 6 July, 2021; v1 submitted 1 July, 2021; originally announced July 2021.

Comments: 26 pages (preprint) and 9 figures

Deconvolution of phonon scattering by ferroelectric domain walls and point defects in a PbTiO3 thin film deposited in a composition-spread geometry

Authors: David Bugallo, Eric Langenberg, Elias Ferreiro-Vila, Eva H. Smith, Christina Stefani, Xavier Batlle, Gustau Catalan, Neus Domingo, Darrell G. Schlom, Francisco Rivadulla

Abstract: We present a detailed analysis of the temperature dependence of the thermal conductivity of a ferroelectric PbTiO3 thin film deposited in a composition-spread geometry enabling a continuous range of compositions from ~25% titanium-deficient to ~20% titanium-rich to be studied. By fitting the experimental results to the Debye model we deconvolve and quantify the two main phonon scattering sources i… ▽ More We present a detailed analysis of the temperature dependence of the thermal conductivity of a ferroelectric PbTiO3 thin film deposited in a composition-spread geometry enabling a continuous range of compositions from ~25% titanium-deficient to ~20% titanium-rich to be studied. By fitting the experimental results to the Debye model we deconvolve and quantify the two main phonon scattering sources in the system: ferroelectric domain walls (DWs) and point defects. Our results prove that ferroelectric DWs are the main agent limiting the thermal conductivity in this system, not only in the stoichiometric region of the thin film ([Pb]/[Ti]~1), but also when the concentration of cation point defects is significant (up to ~15%). Hence, DWs in ferroelectric materials are a source of phonon scattering at least as effective as point defects. Our results demonstrate the viability and effectiveness of using reconfigurable DWs to control the thermal conductivity in solid-state devices. △ Less

Submitted 29 April, 2021; originally announced April 2021.

Lateral electrodeposition of MoS2 semiconductor over an insulator

Authors: Nema Abdelazim, Yasir J Noori, Shibin Thomas, Victoria K Greenacre, Yisong Han, Danielle E. Smith, Giacomo Piana, Nikolay Zhelev, Andrew L. Hector, Richard Beanland, Gillian Reid, Philip N Bartlett, Kees de Groot

Abstract: Developing novel techniques for depositing transition metal dichalcogenides is crucial for the industrial adoption of 2D materials in optoelectronics. In this work, the lateral growth of molybdenum disulfide (MoS2) over an insulating surface is demonstrated using electrochemical deposition. By fabricating a new type of microelectrodes, MoS2 2D films grown from TiN electrodes across opposite sides… ▽ More Developing novel techniques for depositing transition metal dichalcogenides is crucial for the industrial adoption of 2D materials in optoelectronics. In this work, the lateral growth of molybdenum disulfide (MoS2) over an insulating surface is demonstrated using electrochemical deposition. By fabricating a new type of microelectrodes, MoS2 2D films grown from TiN electrodes across opposite sides have been connected over an insulating substrate, hence, forming a lateral device structure through only one lithography and deposition step. Using a variety of characterization techniques, the growth rate of MoS2 has been shown to be highly anisotropic with lateral to vertical growth ratios exceeding 20-fold. Electronic and photo-response measurements on the device structures demonstrate that the electrodeposited MoS2 layers behave like semiconductors, confirming their potential for photodetection applications. This lateral growth technique paves the way towards room temperature, scalable and site-selective production of various transition metal dichalcogenides and their lateral heterostructures for 2D materials-based fabricated devices. △ Less

Submitted 26 November, 2021; v1 submitted 1 April, 2021; originally announced April 2021.

Comments: 8 pages, 5 figures

Path-Dependent Supercooling of the $^3$He Superfluid A-B transition

Authors: Dmytro Lotnyk, Anna Eyal, Nikolay Zhelev, Abhilash Sebastian, Yefan Tian, Aldo Chavez, Eric Smith, John Saunders, Erich Mueller, Jeevak Parpia

Abstract: We examine the discontinuous first-order superfluid $^3$He A to B transition in the vicinity of the polycritical point (2.232 mK and 21.22 bar). We find path-dependent transitions: cooling at fixed pressure yields a well defined transition line in the temperature-pressure plane, but this line can be reliably crossed by depressurizing at nearly constant temperature after transiting $T_{\rm c}$ at a… ▽ More We examine the discontinuous first-order superfluid $^3$He A to B transition in the vicinity of the polycritical point (2.232 mK and 21.22 bar). We find path-dependent transitions: cooling at fixed pressure yields a well defined transition line in the temperature-pressure plane, but this line can be reliably crossed by depressurizing at nearly constant temperature after transiting $T_{\rm c}$ at a higher pressure. This path dependence is not consistent with any of the standard B-phase nucleation mechanisms in the literature. This symmetry breaking transition is a potential simulator for first order transitions in the early universe. △ Less

Submitted 2 April, 2021; v1 submitted 27 December, 2020; originally announced December 2020.

Journal ref: Phys. Rev. Lett. 126, 215301 (2021)

Characterization of a Disordered Above Room Temperature Skyrmion Material Co8Zn8Mn4

Authors: M. E. Henderson, J. Beare, S. Sharma, M. Bleuel, P. Clancy, D. G. Cory, M. G. Huber, C. A. Marjerrison, M. Pula, D. Sarenac, E. M. Smith, K. Zhernenkov, G. M. Luke, D. A. Pushin

Abstract: Topologically non trivial spin textures host great promise for future spintronic applications. Skyrmions in particular are of burgeoning interest owing to their nanometric size, topological protection, and high mobility via ultra-low current densities. It has been previously reported through magnetic susceptibility, microscopy, and scattering techniques that Co$_{8}$Zn$_{8}$Mn$_{4}$ forms an above… ▽ More Topologically non trivial spin textures host great promise for future spintronic applications. Skyrmions in particular are of burgeoning interest owing to their nanometric size, topological protection, and high mobility via ultra-low current densities. It has been previously reported through magnetic susceptibility, microscopy, and scattering techniques that Co$_{8}$Zn$_{8}$Mn$_{4}$ forms an above room temperature triangular skyrmion lattice. Here we report the synthesis procedure and characterization of a polycrystalline Co$_{8}$Zn$_{8}$Mn$_{4}$ bulk sample. We employ powder x-ray diffraction, backscatter Laue diffraction, and neutron diffraction as characterization tools of the crystallinity of the samples, while magnetic susceptibility and Small Angle Neutron Scattering (SANS) measurements are performed to study the skyrmion phase. Magnetic susceptibility measurements show a dip anomaly in the magnetization curves which persists over a range of approximately 305 K- 315 K. SANS measurements reveal a rotationally disordered polydomain skymrion lattice. Applying a recently developed symmetry-breaking magnetic field sequence, we were able to orient and order the previously jammed state to yield the prototypical hexagonal diffraction patterns, with secondary diffraction rings. △ Less

Submitted 21 October, 2020; originally announced October 2020.

Comments: 7 pages, 8 figures

Parallel Spin Stripes and Their Coexistance with Superconducting Ground States at Optimal and High Doping in La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$

Authors: Qianli Ma, Kirrily C. Rule, Zachary W. Cronkwright, Mirela Dragomir, Gabrielle Mitchell, Evan M. Smith, Songxue Chi, Alexander I. Kolesnikov, Matthew B. Stone, Bruce D. Gaulin

Abstract: Quasi-two dimensional quantum magnetism is clearly highly correlated with superconducting ground states in cuprate-based High T$_c$ superconductivity. Three dimensional, commensurate long range magnetic order in La$_2$CuO$_4$ quickly evolves to quasi-two dimensional, incommensurate correlations on doping with mobile holes, and superconducting ground states follow for x as small as 0.05 in the La… ▽ More Quasi-two dimensional quantum magnetism is clearly highly correlated with superconducting ground states in cuprate-based High T$_c$ superconductivity. Three dimensional, commensurate long range magnetic order in La$_2$CuO$_4$ quickly evolves to quasi-two dimensional, incommensurate correlations on doping with mobile holes, and superconducting ground states follow for x as small as 0.05 in the La$_{2-x}$Sr$_x$/Ba$_x$CuO$_4$ family of superconductors. It has long been known that the onset of superconducting ground states in these systems is coincident with a remarkable rotation of the incommensurate spin order from "diagonal stripes" below x = 0.05, to "parallel stripes" above. However, little is known about the spin correlations at optimal and high doping levels, where the dome of superconductivity draws to an end. Here we present new elastic and inelastic neutron scattering measurements on single crystals of La$_{1.6-x}$Nd$_{0.4}$Sr$_x$CuO$_4$ with x = 0.125, 0.19, 0.24 and 0.26, and show that two dimensional, quasi-static, parallel spin stripes are observed to onset at temperatures such that the parallel spin stripe phase envelopes all superconducting ground states in this system. Parallel spin stripes stretch across 0.05 < < 0.26, with rapidly decreasing moment size and onset temperatures for x > 0.125. We also show that the low energy, parallel spin stripe fluctuations for optimally doped x = 0.19 display dynamic spectral weight which grows with decreasing temperature and saturates below its superconducting T$_c$. The elastic order parameter for x = 0.19 also shows plateau behavior coincident with the onset of superconductivity. This set of observations assert the foundational role played by two dimensional parallel spin stripe order and fluctuations in High T$_c$ cuprate superconductivity. △ Less

Submitted 9 September, 2020; originally announced September 2020.

Journal ref: Phys. Rev. Research 3, 023151 (2021)

Eikonal solutions for moment hierarchies of Chemical Reaction Networks in the limits of large particle number

Authors: Eric Smith, Supriya Krishnamurthy

Abstract: Trajectory-based methods are well-developed to approximate steady-state probability distributions for stochastic processes in large-system limits. The trajectories are solutions to equations of motion of Hamiltonian dynamical systems, and are known as eikonals. They also express the leading flow lines along which probability currents balance. The existing eikonal methods for discrete-state process… ▽ More Trajectory-based methods are well-developed to approximate steady-state probability distributions for stochastic processes in large-system limits. The trajectories are solutions to equations of motion of Hamiltonian dynamical systems, and are known as eikonals. They also express the leading flow lines along which probability currents balance. The existing eikonal methods for discrete-state processes including chemical reaction networks are based on the Liouville operator that evolves generating functions of the underlying probability distribution. We have previously derived a representation for the generators of such processes that acts directly in the hierarchy of moments of the distribution, rather than on the distribution itself or on its generating function. We show here how in the large-system limit the steady-state condition for that generator reduces to a mapping from eikonals to the ratios of neighboring factorial moments, as a function of the order $k$ of these moments. The construction shows that the boundary values for the moment hierarchy, and thus its whole solution, are anchored in the interior fixed points of the Hamiltonian system, a result familiar from Freidlin-Wenztell theory. The direct derivation of eikonals from the moment representation further illustrates the relation between coherent-state and number fields in Doi-Peliti theory, clarifying the role of canonical transformations in that theory. △ Less

Submitted 3 August, 2020; originally announced August 2020.

Intrinsic and extrinsic thermodynamics for stochastic population processes with multi-level large-deviation structure

Authors: Eric Smith

Abstract: A set of core features is set forth as the essence of a thermodynamic description, which derive from large-deviation properties in systems with hierarchies of timescales, but which are \emph{not} dependent upon conservation laws or microscopic reversibility in the substrate hosting the process. The most fundamental elements are the concept of a macrostate in relation to the large-deviation entropy… ▽ More A set of core features is set forth as the essence of a thermodynamic description, which derive from large-deviation properties in systems with hierarchies of timescales, but which are \emph{not} dependent upon conservation laws or microscopic reversibility in the substrate hosting the process. The most fundamental elements are the concept of a macrostate in relation to the large-deviation entropy, and the decomposition of contributions to irreversibility among interacting subsystems, which is the origin of the dependence on a concept of heat in both classical and stochastic thermodynamics. A natural decomposition is shown to exist, into a relative entropy and a housekeeping entropy rate, which define respectively the \textit{intensive} thermodynamics of a system and an \textit{extensive} thermodynamic vector embedding the system in its context. Both intensive and extensive components are functions of Hartley information of the momentary system stationary state, which is information \emph{about} the joint effect of system processes on its contribution to irreversibility. Results are derived for stochastic Chemical Reaction Networks, including a Legendre duality for the housekeeping entropy rate to thermodynamically characterize fully-irreversible processes on an equal footing with those at the opposite limit of detailed-balance. The work is meant to encourage development of inherent thermodynamic descriptions for rule-based systems and the living state, which are not conceived as reductive explanations to heat flows. △ Less

Submitted 3 August, 2020; originally announced August 2020.

Effect of an electric field on liquid helium scintillation produced by fast electrons

Authors: N. S. Phan, V. Cianciolo, S. M. Clayton, S. A. Currie, R. Dipert, T. M. Ito, S. W. T. MacDonald, C. M. O'Shaughnessy, J. C. Ramsey, G. M. Seidel, E. Smith, E. Tang, Z. Tang, W. Yao

Abstract: The dependence on applied electric field ($0 - 40$ kV/cm) of the scintillation light produced by fast electrons and $α$ particles stopped in liquid helium in the temperature range of 0.44 K to 3.12 K is reported. For both types of particles, the reduction in the intensity of the scintillation signal due to the applied field exhibits an apparent temperature dependence. Using an approximate solution… ▽ More The dependence on applied electric field ($0 - 40$ kV/cm) of the scintillation light produced by fast electrons and $α$ particles stopped in liquid helium in the temperature range of 0.44 K to 3.12 K is reported. For both types of particles, the reduction in the intensity of the scintillation signal due to the applied field exhibits an apparent temperature dependence. Using an approximate solution of the Debye-Smoluchowski equation, we show that the apparent temperature dependence for electrons can be explained by the time required for geminate pairs to recombine relative to the detector signal integration time. This finding indicates that the spatial distribution of secondary electrons with respect to their geminate partners possesses a heavy, non-Gaussian tail at larger separations, and has a dependence on the energy of the primary ionization electron. We discuss the potential application of this result to pulse shape analysis for particle detection and discrimination. △ Less

Submitted 14 September, 2020; v1 submitted 6 May, 2020; originally announced May 2020.

Journal ref: Phys. Rev. C 102, 035503 (2020)

Thermal transport of helium-3 in a strongly confining channel

Authors: D. Lotnyk, A. Eyal, N. Zhelev, T. S. Abhilash, E. N. Smith, M. Terilli, J. Wilson, E. Mueller, D. Einzel, J. Saunders, J. M. Parpia

Abstract: In a neutral system such as liquid helium-3, transport of mass, heat, and spin provide information analogous to electrical counterparts in metals, superconductors and topological materials. Of particular interest is transport in strongly confining channels of height approaching the superfluid coherence length, where new quantum states are found and excitations bound to surfaces and edges should be… ▽ More In a neutral system such as liquid helium-3, transport of mass, heat, and spin provide information analogous to electrical counterparts in metals, superconductors and topological materials. Of particular interest is transport in strongly confining channels of height approaching the superfluid coherence length, where new quantum states are found and excitations bound to surfaces and edges should be present. Here we report on the thermal conduction of helium-3 in a 1.1~$μ$m high microfabricated channel. In the normal state we observe a diffusive thermal conductivity that is approximately temperature independent, consistent with recent work on the interference of bulk and boundary scattering. In the superfluid state we measure diffusive thermal transport in the absence of thermal counterflow. An anomalous thermal response is also detected in the superfluid which we suggest may arise from a flux of surface excitations. △ Less

Submitted 18 October, 2019; originally announced October 2019.

Comments: A supplement is available. Please contact Jeevak Parpia (jmp9@cornell.edu) if you would like the supplement as well

Spreading of aqueous droplets with common and superspreading surfactants. A molecular dynamics study

Authors: Panagiotis E. Theodorakis, Edward R. Smith, Erich A. Müller

Abstract: The surfactant-driven spreading of droplets is an essential process in many applications ranging from coating flow technology to enhanced oil recovery. Despite the significant advancement in describing spreading processes in surfactant-laden droplets, including the exciting phenomena of superspreading, many features of the underlying mechanisms require further understanding. Here, we have carried… ▽ More The surfactant-driven spreading of droplets is an essential process in many applications ranging from coating flow technology to enhanced oil recovery. Despite the significant advancement in describing spreading processes in surfactant-laden droplets, including the exciting phenomena of superspreading, many features of the underlying mechanisms require further understanding. Here, we have carried out molecular dynamics simulations of a coarse-grained model with a force-field obtained from the statistical associating fluid theory to study droplets laden with common and superspreading surfactants. We have confirmed the important elements of the superspreading mechanism, i.e. the adsorption of surfactant at the contact line and the fast replenishment of surfactant from the bulk. Through a detailed comparison of a range of droplets with different surfactants, our analysis has indicated that the ability of surfactant to adsorb at the interfaces is the key feature of the superspreading mechanism. To this end, surfactants that tend to form aggregates and have a strong hydrophobic attraction in the aggregated cores prevent the fast replenishment of the interfaces, resulting in reduced spreading ability. We also show that various surfactant properties, such as diffusion and architecture, play a secondary role in the spreading process. Moreover, we discuss various drop properties such as the height, contact angle, and surfactant surface concentration, highlighting differences between superspreading and common surfactants. We anticipate that our study will provide further insight for applications requiring the control of wetting. △ Less

Submitted 2 September, 2019; originally announced September 2019.

Comments: 26 pages, 11 figures

Journal ref: Colloids and Surfaces A: Physicochemical and Engineering Aspects 581, 123810 (2019)

The Dirac nodal line network in non-symmorphic rutile semimetal RuO$_2$

Authors: Vedran Jovic, Roland J. Koch, Swarup K. Panda, Helmuth Berger, Philippe Bugnon, Arnaud Magrez, Ronny Thomale, Kevin E. Smith, Silke Biermann, Chris Jozwiak, Aaron Bostwick, Eli Rotenberg, Domenico Di Sante, Simon Moser

Abstract: We employ angle resolved photoemission spectroscopy (ARPES) to investigate the Fermi surface of RuO$_2$. We find a network of two Dirac nodal lines (DNL) as previously predicted in theory, where the valence- and conduction bands touch along continuous lines in momentum space. In addition, we find evidence for a third DNL close to the Fermi level which appears robust despite the presence of signifi… ▽ More We employ angle resolved photoemission spectroscopy (ARPES) to investigate the Fermi surface of RuO$_2$. We find a network of two Dirac nodal lines (DNL) as previously predicted in theory, where the valence- and conduction bands touch along continuous lines in momentum space. In addition, we find evidence for a third DNL close to the Fermi level which appears robust despite the presence of significant spin orbit coupling. We demonstrate that the third DNL gives rise to a topologically trivial flat-band surface state (FBSS) at the (110) surface. This FBSS can be tuned by surface doping and presents an interesting playground for the study of surface chemistry and exotic correlation phenomena. △ Less

Submitted 6 August, 2019; originally announced August 2019.

Comments: 12 pages, 9 figures

The information geometry of 2-field functional integrals

Authors: Eric Smith

Abstract: 2-field functional integrals (2FFI) are an important class of solution methods for generating functions of dissipative processes, including discrete-state stochastic processes, dissipative dynamical systems, and decohering quantum densities. The stationary trajectories of these integrals describe a conserved current by Liouville's theorem, despite the fact that there is no conserved phase space cu… ▽ More 2-field functional integrals (2FFI) are an important class of solution methods for generating functions of dissipative processes, including discrete-state stochastic processes, dissipative dynamical systems, and decohering quantum densities. The stationary trajectories of these integrals describe a conserved current by Liouville's theorem, despite the fact that there is no conserved phase space current in the underlying stochastic process. We develop the information geometry of generating functions for discrete-state classical stochastic processes in the Doi-Peliti 2FFI form, showing that the conserved current is a Fisher information between the underlying distribution of the process and the tilting weight of the generating function. To give an interpretation to the time invertibility implied by current conservation, we use generating functions to represent importance sampling protocols, and show that the conserved Fisher information is the differential of a sample volume under deformations of the nominal distribution and the likelihood ratio. We derive a new pair of dual Riemannian connections respecting the symplectic structure of transport along stationary rays that gives rise to Liouville's theorem, and show that dual flatness in the affine coordinates of the coherent-state basis captures the special role played by coherent states in many 2FFI theories. The covariant convective derivative under time translation correctly represents the geometric invariants of generating functions under canonical transformations of the 2FFI field variables of integration. △ Less

Submitted 21 June, 2019; originally announced June 2019.