Showing 1–35 of 35 results for author: Perera, A

Aqueous-alcohol mixtures in dimension two: miscibility and micro-segregation

Authors: Camille de la Vaissiere, Ayse Butuner, Aurélien Perera

Abstract: Two dimensional site interaction models of water and alcohols are mixed in various proportions and studied by Monte Carlo simulations, with the purpose to clarify problems related to simulation of real micro-heterogeneous systems. Three alcohols are considered, methanol, pentanol and octanol. The main finding is that, while real alcohols demix with water from butanol onward, their 2D analogs are a… ▽ More Two dimensional site interaction models of water and alcohols are mixed in various proportions and studied by Monte Carlo simulations, with the purpose to clarify problems related to simulation of real micro-heterogeneous systems. Three alcohols are considered, methanol, pentanol and octanol. The main finding is that, while real alcohols demix with water from butanol onward, their 2D analogs are always fully miscible, while developing increasingly pronounced micro-segregation as the alcohol tail length increases. This is not a consequence of the intrinsically higher fluctuations in 2D, but rather a reorganization of these fluctuations under the charge ordering mechanism. The second finding is that water drives the micro-segregation through strong self-aggregation, but this is not enough to achieve full phase separation because of the water-alcohol contact at the outer rim of the water domains. In this work we examine how this local heterogeneity develops with increasing alcohol alkyl tails, monitored with the study of pair correlation functions, structure factors and Kirkwood-Buff integrals. The absence of clear local self-averaging of the latter provides an illustration of the tension between energy driven maintaining of local structures and entropy driven global homogeneity. In that, the 2D modelisation of real hydrogen bonding mixtures allows to better capture and reveal the physics behind the chemistry of these liquids. △ Less

Submitted 4 June, 2026; originally announced June 2026.

Comments: 24 pages, 17 fgures

Charge order, domain order, ideal mixing and absence of demixing in 2D binary mixtures of alcohols

Authors: Lydia Chelli, Aurélien Perera

Abstract: Binary mixtures of two dimensional, site-based models of alcohols are investigated by computer simulations, with a focus on ideal mixing, local clustering and miscibility trends. Four representative systems are considered: methanol/ethanol, butanol/pentanol, methanol/pentanol, and methanol/octanol. The models retain chemical specificity, while allowing to investigate dimensional constraints and un… ▽ More Binary mixtures of two dimensional, site-based models of alcohols are investigated by computer simulations, with a focus on ideal mixing, local clustering and miscibility trends. Four representative systems are considered: methanol/ethanol, butanol/pentanol, methanol/pentanol, and methanol/octanol. The models retain chemical specificity, while allowing to investigate dimensional constraints and uncover non/trivial micro/structurations. Two unexpected results are observed. First, mixtures of short and long alcohols are well mixed, instead of the macroscopic phase separation found in their three-dimensional counterparts. Second, ideality and micro phase separation compete within the chain like polar head aggregates. These behaviors cannot be explained solely by enhanced fluctuations in two dimensions, and instead point to a key role of charge ordering in shaping the local structure. The resulting interplay between concentration fluctuations and micro heterogeneous aggregation is analyzed through snapshots, site/site distribution functions, structure factors and Kirkwood Buff integrals. In particular, the analysis reveals that the domain correlations in the long range part of the correlations have an intriguing non self averaging behaviour, similar to that found in the real systems, indicating that mixtures of associating molecules are not ruled by conventional fluctuations. △ Less

Submitted 24 April, 2026; originally announced April 2026.

Comments: 25 pages, 15 figures

On the performance of QTP functionals applied to second-order response properties II: Dynamic polarizability and long-range C$_6$ coefficients

Authors: Rodrigo A. Mendes, Peter R. Franke, Ajith Perera, Rodney J. Bartlett

Abstract: This work is the second in the series "On the performance of QTP functionals applied to second-order response properties." In the first paper (J. Chem. Phys. 162, 054105, 2025), we demonstrated the good performance of Quantum Theory Project functionals in predicting static perturbed second-order properties, such as static polarizabilities, nuclear magnetic resonance (NMR) spin-spin coupling consta… ▽ More This work is the second in the series "On the performance of QTP functionals applied to second-order response properties." In the first paper (J. Chem. Phys. 162, 054105, 2025), we demonstrated the good performance of Quantum Theory Project functionals in predicting static perturbed second-order properties, such as static polarizabilities, nuclear magnetic resonance (NMR) spin-spin coupling constants, and NMR chemical shifts. In the present study, we focus on frequency-dependent properties, namely dynamic polarizabilities and C$_6$ dispersion coefficients. For completeness, a total of 25 exchange-correlation (XC) functionals were investigated. Dynamic polarizabilities were evaluated at five different perturbation wavelengths: 632.99 nm, 594.10 nm, 543.52 nm, 514.50 nm, and 325.13 nm. This property was also computed using HF and EOM-CCSD. In general, EOM-CCSD results are very close to those obtained with linear-response CC3, except at the highest frequency. Among Kohn-Sham calculations, TPSS0 and QTP01 showed the best overall performance for dynamic polarizabilities. We also assessed how well QTP functionals reproduce the pole structure of the CO molecule. For the C$_6$ dispersion coefficients, calculations were performed using the Casimir-Polder equation. The best overall performance was obtained with O3LYP; however, the first eleven ranked functionals show very similar accuracy. Within the QTP family, QTP01 and LC-QTP provide the best results for C$_6$ coefficients. △ Less

Submitted 12 May, 2026; v1 submitted 16 March, 2026; originally announced March 2026.

Mesoscopic Correlations in Aqueous Alkylamine Mixtures Between Molecular and Micro Emulsions

Authors: Aurelien Perera

Abstract: Understanding how molecular correlations give rise to mesoscale organization is central to the physics of complex fluids such as hydrogen-bonded mixtures. In this work, we develop a mesoscale bridge formalism that connects the site-site Ornstein-Zernike (SSOZ) framework to the field theoretical Teubner-Strey (TS) approach. This bridge highlights how local orientational correlations, typically lost… ▽ More Understanding how molecular correlations give rise to mesoscale organization is central to the physics of complex fluids such as hydrogen-bonded mixtures. In this work, we develop a mesoscale bridge formalism that connects the site-site Ornstein-Zernike (SSOZ) framework to the field theoretical Teubner-Strey (TS) approach. This bridge highlights how local orientational correlations, typically lost in the SSOZ closure, reemerge as effective long-range components at the mesoscale. The resulting theory provides a unified description of density fluctuations spanning molecular to mesoscopic length scales. The approach is illustrated using X-ray scattering spectra from simulated and experimental hydrogen-bonded fluids, showing that the TS representation captures the essential features of the mesoscale structure. Beyond this specific application, the proposed formalism offers a general route to interpret the structural crossover between microscopic interactions and collective mesoscale organization in complex fluids, including aqueous and amphiphilic systems. △ Less

Submitted 11 November, 2025; originally announced November 2025.

Microscopic Structure of Aqueous Alkylamine mixtures: a Computer Simulation Study

Authors: Martina Požar, Lena Friedrich, Bernarda Lovrinčević, Michael Paulus, Christian Sternemann, Aurélien Perera

Abstract: Aqueous alkylamine mixtures are studied by computer simulations in order to understand the microscopic origin of the water rich side prominent x-ray scattering pre-peaks reported in a recent study. These pre-peaks are puzzling in view of the apparently contradicting facts that neat amines show pre-peaks much weaker than neat alkanols, while water-rich aqueous alcohols do not. These observations ca… ▽ More Aqueous alkylamine mixtures are studied by computer simulations in order to understand the microscopic origin of the water rich side prominent x-ray scattering pre-peaks reported in a recent study. These pre-peaks are puzzling in view of the apparently contradicting facts that neat amines show pre-peaks much weaker than neat alkanols, while water-rich aqueous alcohols do not. These observations can be intuitively rationalized by noting that the amine head group have two hydrogen atoms when the hydroxyl group have only one, but they oppose the following two facts: i) computer simulations show micro-heterogeneity for both systems; ii) amines mix with water better than alcohols, both over larger concentrations and alkyl tails lengths. The study of the atom-atom pair correlation functions and related structure factors allows to understand the microscopic molecular details. The most interesting observation is that the amine head groups accumulate preferentially at the surface of the water domains, and increasingly better with longer alkyl tail, thus allowing to stabilize both the water and alkylamine domains, hence avoiding macroscopic demixing, except at high water concentrations when amines are scarce to achieve efficient surface saturation. The amine domains appear as disordered bilayers. Hence, aqueous amines are analogous to an inverse micelle melt and as precursor micro-emulsion. This stable micro-segregation produces large domain oscillations in the long range part of the correlation functions, translating into positive pre-peaks and negative anti-peaks in the related structure factors, the latter which contribute destructively to produce the prominent scattering pre-peak observed in the x-ray experiments. The model dependence is shown to be quite important, both for water and solute models. The CHARMM-AA model associated with the SPC/E model seems to be a good compromise. △ Less

Submitted 2 October, 2025; originally announced October 2025.

Site-site interaction model for alcohol models in two-dimensions

Authors: Aurélien Perera

Abstract: An interaction site-based model of two-dimensional alcohols is proposed as a follow up of the recent SSMB site-site model for 2D water [J. Mol. Liq. 386 (2023 122475]. Computer simulation studies indicate that the model exhibits hbond-type clustering based on the same charge order feature observed in real alcohols. Hence, the equivalent of 2D mono-ols ranging from methanol to octanol were studied… ▽ More An interaction site-based model of two-dimensional alcohols is proposed as a follow up of the recent SSMB site-site model for 2D water [J. Mol. Liq. 386 (2023 122475]. Computer simulation studies indicate that the model exhibits hbond-type clustering based on the same charge order feature observed in real alcohols. Hence, the equivalent of 2D mono-ols ranging from methanol to octanol were studied for their clustering properties, focusing on how the micro-structure affects the shape of the site-site pair correlation functions and structure factors, as well as the combination of the latter into the radiation scattering intensities. The major finding is the apparent contradiction between the existence of large pre-peaks in the structure factors, usually associated to the existence of clusters, and the exponential decay of the cluster distribution indicating the absence of specific clusters, contrary to the 3D case. This is resolved by realizing that the pair correlation function is an observable of the local density fluctuations, hence the pre-peak witnesses fluctuations around clustering tendencies, which are the result of charge ordering of the polar groups, and visible in the snapshots. The scattering pre-peak witnesses only fluctuations due to charge ordering, and not the clusters themselves, underlining the fact that these are labile entities. The study highlights how charge order through atomic sites is a universal feature behind the micro-structure of organized liquids, and, in the particular case of 2D liquids, a more realistic alternative to orientation based models such as the Mercedes-Benz model, for instance. △ Less

Submitted 23 September, 2024; originally announced September 2024.

On the microscopic structure of neat linear alkylamine liquids: an x-ray scattering and computer simulation study

Authors: Martina Požar, Lena Friedrich, Tristan Millet, Michael Paulus, Christian Sternemann, Aurélien Perera

Abstract: Ambient condition linear amines, from propylamine up to nonylamine, are studied by x-ray scattering and Molecular Dynamics simulations of various force field models. The major finding is that the pre-peak in alkylamines is of about one order of magnitude weaker than that in alkanols, hence suggesting much weaker hydrogen bonding induced clustering of the amine groups than for the hydroxyl groups.… ▽ More Ambient condition linear amines, from propylamine up to nonylamine, are studied by x-ray scattering and Molecular Dynamics simulations of various force field models. The major finding is that the pre-peak in alkylamines is of about one order of magnitude weaker than that in alkanols, hence suggesting much weaker hydrogen bonding induced clustering of the amine groups than for the hydroxyl groups. Computer simulation studies reveal that OPLS-UA model reproduces the pre-peak, but with larger amplitudes, while the GROMOS-UA and CHARMM-AA force fields show almost no pre-peak. Simulations of all models reveal the existence of hydrogen bonded clusters, equally confirmed through the prominent pre-peak of the structure factor between the nitrogen atoms. But, this pre-peak gets nearly cancelled by the various combinations of the atom-atom structure factors contributions to the scattering intensity, except for the OPLS model. The purpose of this work is to understand the weakness of the scattering pre-peak from the pair correlation function perspective, considered as an order parameter associated to the concept of charge order. The difference between models is equally analyzed from the same perspective. The analysis reveals the strong charge order induced structural similarity between amines and water, as opposed to mono-ols. This is traced back to the C2v symmetry of both the water molecule and the amine head group. It explains both the existence of H-bonded clusters and the weak scattering pre-peak. Concerning the models, the presence or absence of partial charges in the methyl groups of the alkyl tails explains the presence or absence of the pre-peak in the calculated scattering intensities △ Less

Submitted 19 July, 2024; originally announced July 2024.

An "ultimate" coupled cluster method based entirely on $T_2$

Authors: Zachary W. Windom, Ajith Perera, Rodney J. Bartlett

Abstract: Electronic structure methods built around double-electron excitations have a rich history in quantum chemistry. However, it seems to be the case that such methods are only suitable in particular situations and are not naturally equipped to simultaneously handle the variety of electron correlations that might be present in chemical systems. To this end, the current work seeks a computationally effi… ▽ More Electronic structure methods built around double-electron excitations have a rich history in quantum chemistry. However, it seems to be the case that such methods are only suitable in particular situations and are not naturally equipped to simultaneously handle the variety of electron correlations that might be present in chemical systems. To this end, the current work seeks a computationally efficient, low-rank, "ultimate" coupled cluster method based exclusively on $T_2$ and its products which can effectively emulate more "complete" methods that explicitly consider higher-rank, $T_{2m}$ operators. We introduce a hierarchy of methods designed to systematically account for higher, even order cluster operators - like $T_4, T_6, \cdots, T_{2m}$ - by invoking tenets of the factorization theorem of perturbation theory and expectation-value coupled cluster theory. It is shown that each member within this methodological hierarchy is defined such that both the wavefunction and energy are correct through some order in many-body perturbation theory (MBPT), and can be extended up to arbitrarily high orders in $T_2$. The efficacy of such approximations are determined by studying the potential energy surface of several prototypical systems that are chosen to represent both non-dynamic, static, and dynamic correlation regimes. We find that the proposed hierarchy of augmented $T_2$ methods essentially reduce to standard CCD for problems where dynamic electron correlations dominate, but offer improvements in situations where non-dynamic and static correlations become relevant. A notable highlight of this work is that the cheapest methods in this hierarchy - which are correct through fifth-order in MBPT - consistently emulate the behavior of the $\mathcal{O}(N^{10})$ CCDQ method, yet only require a $\mathcal{O}(N^{6})$ algorithm by virtue of factorized intermediates. △ Less

Submitted 11 July, 2024; originally announced July 2024.

An assessment of frozen natural orbitals and band gaps using equation of motion coupled cluster theory: a case study on polyacene and trans-polyacetylene

Authors: Zachary W. Windom, AV Lam, Ajith Perera, Rodney J. Bartlett

Abstract: Frozen natural orbitals (FNOs) are used to augment IP/EA-EOM-CCSD calculations targeting the band gap of trans-polyacetylene and polyacene. We show the resulting electron affinities (EAs), ionization potentials (IPs), and extrapolated band gaps incur errors that are largely tunable to a desired accuracy, yet require many orders of magnitude fewer core-hours as compared to the corresponding full ca… ▽ More Frozen natural orbitals (FNOs) are used to augment IP/EA-EOM-CCSD calculations targeting the band gap of trans-polyacetylene and polyacene. We show the resulting electron affinities (EAs), ionization potentials (IPs), and extrapolated band gaps incur errors that are largely tunable to a desired accuracy, yet require many orders of magnitude fewer core-hours as compared to the corresponding full calculation. The relationship between various FNO truncation schemes and (cc-pV$n$Z) basis set is also examined. △ Less

Submitted 13 February, 2024; originally announced February 2024.

The influence of charge ordering in the microscopic structure of monohydroxy alcohols

Authors: Martina Požar, Bernarda Lovrinčević, Aurélien Perera

Abstract: While radiation scattering data provides insight inside the microstructure of liquids, the Debye relation relating the scattering intensity $I(k)$ to the atom-atom structure factors $S_{ab}(k)$ shows that, ultimately, it is these individual structure correlation functions which contain the relevant information about the micro-structure. However, these quantities are not observables, except in few… ▽ More While radiation scattering data provides insight inside the microstructure of liquids, the Debye relation relating the scattering intensity $I(k)$ to the atom-atom structure factors $S_{ab}(k)$ shows that, ultimately, it is these individual structure correlation functions which contain the relevant information about the micro-structure. However, these quantities are not observables, except in few cases where one can invert the Debye relation in order to obtain the structure functions. In the majority of other cases, the need for model dependent computer simulations is unavoidable. The resulting calculations reveal that the scattering pre-peak is the result of cancellations between positive pre-peaks and negative anti-peaks contributions from the atom-atom structure factors. What of systems where this cancellation is such that it entirely suppresses the scattering pre-peak? One would be tempted to falsely conclude that there is no uderlying micro-heterogeneity. Hence, the structure functions appear as hidden variables, and it is important to understand the relation between their features and the micro-structure of the system. Through the computer simulation study of various mono-ols, ranging from methanol to 1-nonanol, as well as the branched octanols, we show how the features of the atom-atom pair correlation function $g_{ab}(r)$ affect that of the structure factors $S_{ab}(k)$, and reveal that the micro-structure is ultimately the result of the charge ordering between different atoms in the system. △ Less

Submitted 1 June, 2023; originally announced June 2023.

Comments: 24 pages, 12 figures

Dynamical correlations in simple disorder and complex disorder liquid

Authors: Bernarda Lovrinčević, Martina Požar, Ivo Jukić, David Perera, Aurélien Perera

Abstract: Liquids in equilibrium exhibit two types of disorder, simple and complex. Typical simple disorder liquid are liquid nitrogen, or weakly polar liquids. Complex liquids concern those who can form long lived local assemblies, and cover a large range from water to soft matter and biological liquids. The existence of such structures leaves characteric features upon the atom-atom correlation functions,… ▽ More Liquids in equilibrium exhibit two types of disorder, simple and complex. Typical simple disorder liquid are liquid nitrogen, or weakly polar liquids. Complex liquids concern those who can form long lived local assemblies, and cover a large range from water to soft matter and biological liquids. The existence of such structures leaves characteric features upon the atom-atom correlation functions, concerning both atoms which directly participate to these structure and those who do not. The question we ask here is: does these features have also characteristic dynamical aspects, which could be tracked through dynamical correlation functions. Herein, we compare the van Hove function, intermediate scattering function and the dynamical structure factor, for both types of liquids, using force field models and computer simulations. The calculations reveal the paradoxical fact that neighbouring atom correlations for simple disorder liquids relax slower than that for complex disorder liquids, while prepeak features typical of complex disorder liquids relax even slower. This is an indication of the existence of fast kinetic self-assembly processes in complex disorder liquids, while the lifetime of such assemblies itself is quite slow. This is further confirmed by the existence of a very low-k dynamical pre-peak uncovered in the case of water and ethanol. △ Less

Submitted 1 June, 2023; originally announced June 2023.

Comments: 33 pages, 16 figures

A site-site interaction two-dimensional model with water like structural properties

Authors: Tangi Baré, Maxime Besserve, Tomaz Urbic, Aurélien Perera

Abstract: A site-site interaction model is proposed for water in two-dimension, as an alternative to the traditional Mercedes-Benz model. In MB model, water molecules are modeled as 2-dimensional Lennard-Jones disks with three hydrogen bonding arms arranged symmetrically, resembling the Mercedes-Benz logo. The MB model qualitatively predicts both the anomalous properties of pure water and the anomalous solv… ▽ More A site-site interaction model is proposed for water in two-dimension, as an alternative to the traditional Mercedes-Benz model. In MB model, water molecules are modeled as 2-dimensional Lennard-Jones disks with three hydrogen bonding arms arranged symmetrically, resembling the Mercedes-Benz logo. The MB model qualitatively predicts both the anomalous properties of pure water and the anomalous solvation thermodynamics of non-polar molecules. One of the features of this earlier model was to have a pair correlation function with first peak for the Lennard-Jones contact distinct of that corresponding to the hydrogen bonding, which is very different from real water which has a single first peak, but a dual peak for the structure factor. The site-site model proposed here reproduces this typical feature of real water, both in real and reciprocal space. It also reproduces several of the known anomalies of real water, such as the density maximum. In addition, because of the screened Coulomb interaction between the sites, the new model appear to exhibit more homogeneity that the MB models and their variants, the latter which is highlighted by a k=0 increase of their structure factors. The new model transfers the usual bond order paradigm into a charge order paradigm, enforcing atom-atom interactions over orientational interactions. △ Less

Submitted 1 June, 2023; originally announced June 2023.

Comments: 24 pages, 17 figures

The AWAKE Run 2 programme and beyond

Authors: Edda Gschwendtner, Konstantin Lotov, Patric Muggli, Matthew Wing, Riccardo Agnello, Claudia Christina Ahdida, Maria Carolina Amoedo Goncalves, Yanis Andrebe, Oznur Apsimon, Robert Apsimon, Jordan Matias Arnesano, Anna-Maria Bachmann, Diego Barrientos, Fabian Batsch, Vittorio Bencini, Michele Bergamaschi, Patrick Blanchard, Philip Nicholas Burrows, Birger Buttenschön, Allen Caldwell, James Chappell, Eric Chevallay, Moses Chung, David Andrew Cooke, Heiko Damerau , et al. (77 additional authors not shown)

Abstract: Plasma wakefield acceleration is a promising technology to reduce the size of particle accelerators. Use of high energy protons to drive wakefields in plasma has been demonstrated during Run 1 of the AWAKE programme at CERN. Protons of energy 400 GeV drove wakefields that accelerated electrons to 2 GeV in under 10 m of plasma. The AWAKE collaboration is now embarking on Run 2 with the main aims to… ▽ More Plasma wakefield acceleration is a promising technology to reduce the size of particle accelerators. Use of high energy protons to drive wakefields in plasma has been demonstrated during Run 1 of the AWAKE programme at CERN. Protons of energy 400 GeV drove wakefields that accelerated electrons to 2 GeV in under 10 m of plasma. The AWAKE collaboration is now embarking on Run 2 with the main aims to demonstrate stable accelerating gradients of 0.5-1 GV/m, preserve emittance of the electron bunches during acceleration and develop plasma sources scalable to 100s of metres and beyond. By the end of Run 2, the AWAKE scheme should be able to provide electron beams for particle physics experiments and several possible experiments have already been evaluated. This article summarises the programme of AWAKE Run 2 and how it will be achieved as well as the possible application of the AWAKE scheme to novel particle physics experiments. △ Less

Submitted 13 June, 2022; originally announced June 2022.

Comments: 21 pages, 8 figures. Submitted to Symmetry journal

Camel back shaped Kirkwood-Buff Integrals

Authors: Aurélien Perera, Martina Požar, Bernarda Lovrinčević

Abstract: Some binary mixtures, such as specific alcohol-alkane mixtures, or even water-tbutanol, exhibit two humps camel back shaped KBI. This is in sharp contrast with usual KBI of binary mixtures having a single extremum. This extremum is interpreted as the region of maximum concentration fluctuations, and usually occurs in binary mixtures presenting appreciable micro-segregation, and corresponds to wher… ▽ More Some binary mixtures, such as specific alcohol-alkane mixtures, or even water-tbutanol, exhibit two humps camel back shaped KBI. This is in sharp contrast with usual KBI of binary mixtures having a single extremum. This extremum is interpreted as the region of maximum concentration fluctuations, and usually occurs in binary mixtures presenting appreciable micro-segregation, and corresponds to where the mixture exhibit a percolation of the two species domains. In this paper, it is shown that two extrema occur in binary mixtures when one species forms "meta-particle" aggregates, the latter which act as a meta-species, and have their own concentration fluctuations, hence their own KBI extremum. This "meta-extremum" occurs at low concentration of the aggregate-forming species (such as alcohol in alkane), and is independant of the other usual extremum observed at mid volume fraction occupancy. These systems are a good illustration of the concept of the duality between concentration fluctuations and micro-segregation. △ Less

Submitted 7 January, 2022; originally announced January 2022.

An Innovative Transverse Emittance Cooling Technique using a Laser-Plasma Wiggler

Authors: Oznur Apsimon, Daniel Seipt, Monika Yadav, Aravinda Perera, Yong Ma, Dino Jaroszynski, Alec Thomas, Guoxing Xia, Carsten Welsch

Abstract: We propose an innovative beam cooling scheme based on laser driven plasma wakefields to address the challenge of high luminosity generation for a future linear collider. For linear colliders, beam cooling is realised by means of damping rings equipped with wiggler magnets and accelerating cavities. This scheme ensures systematic reduction of phase space volume through synchrotron radiation emissio… ▽ More We propose an innovative beam cooling scheme based on laser driven plasma wakefields to address the challenge of high luminosity generation for a future linear collider. For linear colliders, beam cooling is realised by means of damping rings equipped with wiggler magnets and accelerating cavities. This scheme ensures systematic reduction of phase space volume through synchrotron radiation emission whilst compensating for longitudinal momentum loss via an accelerating cavity. In this paper, the concept of a plasma wiggler and its effective model analogous to a magnetic wiggler are introduced; relation of plasma wiggler characteristics with damping properties are demonstrated; underpinning particle-in-cell simulations for laser propagation optimisation are presented. The oscillation of transverse wakefields and resulting sinusoidal probe beam trajectory are numerically demonstrated. The formation of an order of magnitude larger effective wiggler field compared to conventional wigglers is successfully illustrated. Potential damping ring designs on the basis of this novel plasma-based technology are presented and performance in terms of damping times and footprint was compared to an existing conventional damping ring design. △ Less

Submitted 15 December, 2021; originally announced December 2021.

Analysis of Proton Bunch Parameters in the AWAKE Experiment

Authors: V. Hafych, A. Caldwell, R. Agnello, C. C. Ahdida, M. Aladi, M. C. Amoedo Goncalves, Y. Andrebe, O. Apsimon, R. Apsimon, A. -M. Bachmann, M. A. Baistrukov, F. Batsch, M. Bergamaschi, P. Blanchard, P. N. Burrows, B. Buttenschön, J. Chappell, E. Chevallay, M. Chung, D. A. Cooke, H. Damerau, C. Davut, G. Demeter, A. Dexter, S. Doebert , et al. (63 additional authors not shown)

Abstract: A precise characterization of the incoming proton bunch parameters is required to accurately simulate the self-modulation process in the Advanced Wakefield Experiment (AWAKE). This paper presents an analysis of the parameters of the incoming proton bunches used in the later stages of the AWAKE Run 1 data-taking period. The transverse structure of the bunch is observed at multiple positions along t… ▽ More A precise characterization of the incoming proton bunch parameters is required to accurately simulate the self-modulation process in the Advanced Wakefield Experiment (AWAKE). This paper presents an analysis of the parameters of the incoming proton bunches used in the later stages of the AWAKE Run 1 data-taking period. The transverse structure of the bunch is observed at multiple positions along the beamline using scintillating or optical transition radiation screens. The parameters of a model that describes the bunch transverse dimensions and divergence are fitted to represent the observed data using Bayesian inference. The analysis is tested on simulated data and then applied to the experimental data. △ Less

Submitted 27 September, 2021; originally announced September 2021.

Simulation and Experimental Study of Proton Bunch Self-Modulation in Plasma with Linear Density Gradients

Authors: P. I. Morales Guzmán, P. Muggli, R. Agnello, C. C. Ahdida, M. Aladi, M. C. Amoedo Goncalves, Y. Andrebe, O. Apsimon, R. Apsimon, A. -M. Bachmann, M. A. Baistrukov, F. Batsch, M. Bergamaschi, P. Blanchard, F. Braunmüller, P. N. Burrows, B. Buttenschön, A. Caldwell, J. Chappell, E. Chevallay, M. Chung, D. A. Cooke, H. Damerau, C. Davut, G. Demeter , et al. (66 additional authors not shown)

Abstract: We present numerical simulations and experimental results of the self-modulation of a long proton bunch in a plasma with linear density gradients along the beam path. Simulation results agree with the experimental results reported in arXiv:2007.14894v2: with negative gradients, the charge of the modulated bunch is lower than with positive gradients. In addition, the bunch modulation frequency vari… ▽ More We present numerical simulations and experimental results of the self-modulation of a long proton bunch in a plasma with linear density gradients along the beam path. Simulation results agree with the experimental results reported in arXiv:2007.14894v2: with negative gradients, the charge of the modulated bunch is lower than with positive gradients. In addition, the bunch modulation frequency varies with gradient. Simulation results show that dephasing of the wakefields with respect to the relativistic protons along the plasma is the main cause for the loss of charge. The study of the modulation frequency reveals details about the evolution of the self-modulation process along the plasma. In particular for negative gradients, the modulation frequency across time-resolved images of the bunch indicates the position along the plasma where protons leave the wakefields. Simulations and experimental results are in excellent agreement. △ Less

Submitted 23 July, 2021; originally announced July 2021.

Comments: 13 pages, 11 figures

Journal ref: Phys. Rev. Accel. Beams 24, 101301 (2021)

Modeling Betatron Radiation Diagnostics for E-310 -- Trojan Horse

Authors: M. Yadav, C. Hansel, Y. Zhuang, B. Naranjo, N. Majernik, A. Perera, Y. Sakai, G. Andonian, O. Williams, P. Manwani, J. Resta-Lopez, O. Apsimon, C. Welsch, B. Hidding, J. Rosenzweig

Abstract: The E-310 experiment at the Facility for Advanced Accelerator Experimental Tests II (FACET-II) at SLAC National Accelerator Laboratory aims to demonstrate the creation of high brightness beams from a plasma photocathode. Betatron radiation will be measured by a Compton spectrometer, currently under development at UCLA, to provide single-shot, nondestructive beam diagnostics. We give a brief overvi… ▽ More The E-310 experiment at the Facility for Advanced Accelerator Experimental Tests II (FACET-II) at SLAC National Accelerator Laboratory aims to demonstrate the creation of high brightness beams from a plasma photocathode. Betatron radiation will be measured by a Compton spectrometer, currently under development at UCLA, to provide single-shot, nondestructive beam diagnostics. We give a brief overview of this spectrometer as well as double differential spectrum reconstruction from the spectrometer image and beam parameter reconstruction from this double differential spectrum. We discuss three models for betatron radiation: an idealized particle tracking code which computes radiation from Liénard-Wiechert potentials, a quasi-static particle-in-cell (PIC) code which computes radiation from Liénard-Wiechert potentials, and a full PIC code which computes radiation using a Monte Carlo QED method. Spectra computed by the three models for a simple case are compared. △ Less

Submitted 30 June, 2021; originally announced July 2021.

Comments: Proceedings of the Advanced Accelerator Concepts Seminar Series 2020

Universal features in lifetime distribution of clusters in hydrogen bonding liquids

Authors: Ivo Jukic, Bernarda Lovrinvevic, Martina Pozar, Aurélien Perera

Abstract: Hydrogen bonding liquids, typically water and alcohols, are known to form labile structures (network, chains, etc...), hence the lifetime of such structures is an important microscopic parameter, which can be calculated in computer simulations. Since these cluster entities are mostly statistical in nature, one would expect that, in the short time regime, their lifetime distribution would be a broa… ▽ More Hydrogen bonding liquids, typically water and alcohols, are known to form labile structures (network, chains, etc...), hence the lifetime of such structures is an important microscopic parameter, which can be calculated in computer simulations. Since these cluster entities are mostly statistical in nature, one would expect that, in the short time regime, their lifetime distribution would be a broad Gaussian-like function of time, with a single maximum representing their mean lifetime, and weakly dependent on criteria such as the bonding distance and angle, much similarly to non-hydrogen bonding simple liquids, while the long time part is known to have some power law dependence. Unexpectedly, all the hydrogen bonding liquids studied herein, namely water and alcohols, display highly hierarchic three types of specific lifetimes, in the sub-picosecond range 0-0.5ps The dominant lifetime very strongly depends on the bonding distance criterion and is related to hydrogen bonded pairs. This mode is absent in non-H-bonding simple liquids. The secondary and tertiary mean lifetimes are related to clusters, and are nearly independent on the bonding criterion. Of these two lifetimes, only the first one can be related to that of simple liquids, which poses the question of the nature of the third life time. The study of acohols reveals that this 3rd lifetime is related to the topology of H-bonded clusters, and that its distribution may be also affected by the alkyl tail surrounding "bath". This study reveals that hydrogen bonding liquids have a universal hierarchy of hydrogen bonding lifetimes with a timescale regularity across very different types, and which depend on the topology of the cluster structures △ Less

Submitted 7 May, 2021; originally announced May 2021.

Comments: 20 pages, 9 figures, paper

Transition between Instability and Seeded Self-Modulation of a Relativistic Particle Bunch in Plasma

Authors: F. Batsch, P. Muggli, R. Agnello, C. C. Ahdida, M. C. Amoedo Goncalves, Y. Andrebe, O. Apsimon, R. Apsimon, A. -M. Bachmann, M. A. Baistrukov, P. Blanchard, F. Braunmüller, P. N. Burrows, B. Buttenschön, A. Caldwell, J. Chappell, E. Chevallay, M. Chung, D. A. Cooke, H. Damerau, C. Davut, G. Demeter, H. L. Deubner, S. Doebert, J. Farmer , et al. (72 additional authors not shown)

Abstract: We use a relativistic ionization front to provide various initial transverse wakefield amplitudes for the self-modulation of a long proton bunch in plasma. We show experimentally that, with sufficient initial amplitude ($\ge(4.1\pm0.4)$ MV/m), the phase of the modulation along the bunch is reproducible from event to event, with 3 to 7% (of 2$π$) rms variations all along the bunch. The phase is not… ▽ More We use a relativistic ionization front to provide various initial transverse wakefield amplitudes for the self-modulation of a long proton bunch in plasma. We show experimentally that, with sufficient initial amplitude ($\ge(4.1\pm0.4)$ MV/m), the phase of the modulation along the bunch is reproducible from event to event, with 3 to 7% (of 2$π$) rms variations all along the bunch. The phase is not reproducible for lower initial amplitudes. We observe the transition between these two regimes. Phase reproducibility is essential for deterministic external injection of particles to be accelerated. △ Less

Submitted 17 December, 2020; originally announced December 2020.

Comments: Letter and Supplemental Material, 6 figures, 8 pages

Journal ref: Phys. Rev. Lett. 126, 164802 (2021)

Experimental study of extended timescale dynamics of a plasma wakefield driven by a self-modulated proton bunch

Authors: J. Chappell, E. Adli, R. Agnello, M. Aladi, Y. Andrebe, O. Apsimon, R. Apsimon, A. -M. Bachmann, M. A. Baistrukov, F. Batsch, M. Bergamaschi, P. Blanchard, P. N. Burrows, B. Buttenschön, A. Caldwell, E. Chevallay, M. Chung, D. A. Cooke, H. Damerau, C. Davut, G. Demeter, L. H. Deubner, A. Dexter, G. P. Djotyan, S. Doebert , et al. (74 additional authors not shown)

Abstract: Plasma wakefield dynamics over timescales up to 800 ps, approximately 100 plasma periods, are studied experimentally at the Advanced Wakefield Experiment (AWAKE). The development of the longitudinal wakefield amplitude driven by a self-modulated proton bunch is measured using the external injection of witness electrons that sample the fields. In simulation, resonant excitation of the wakefield cau… ▽ More Plasma wakefield dynamics over timescales up to 800 ps, approximately 100 plasma periods, are studied experimentally at the Advanced Wakefield Experiment (AWAKE). The development of the longitudinal wakefield amplitude driven by a self-modulated proton bunch is measured using the external injection of witness electrons that sample the fields. In simulation, resonant excitation of the wakefield causes plasma electron trajectory crossing, resulting in the development of a potential outside the plasma boundary as electrons are transversely ejected. Trends consistent with the presence of this potential are experimentally measured and their dependence on wakefield amplitude are studied via seed laser timing scans and electron injection delay scans. △ Less

Submitted 12 October, 2020; originally announced October 2020.

Comments: 11 pages, 8 figures

Proton beam defocusing in AWAKE: comparison of simulations and measurements

Authors: A. A. Gorn, M. Turner, E. Adli, R. Agnello, M. Aladi, Y. Andrebe, O. Apsimon, R. Apsimon, A. -M. Bachmann, M. A. Baistrukov, F. Batsch, M. Bergamaschi, P. Blanchard, P. N. Burrows, B. Buttenschon, A. Caldwell, J. Chappell, E. Chevallay, M. Chung, D. A. Cooke, H. Damerau, C. Davut, G. Demeter, L. H. Deubner, A. Dexter , et al. (74 additional authors not shown)

Abstract: In 2017, AWAKE demonstrated the seeded self-modulation (SSM) of a 400 GeV proton beam from the Super Proton Synchrotron (SPS) at CERN. The angular distribution of the protons deflected due to SSM is a quantitative measure of the process, which agrees with simulations by the two-dimensional (axisymmetric) particle-in-cell code LCODE. Agreement is achieved for beam populations between $10^{11}$ and… ▽ More In 2017, AWAKE demonstrated the seeded self-modulation (SSM) of a 400 GeV proton beam from the Super Proton Synchrotron (SPS) at CERN. The angular distribution of the protons deflected due to SSM is a quantitative measure of the process, which agrees with simulations by the two-dimensional (axisymmetric) particle-in-cell code LCODE. Agreement is achieved for beam populations between $10^{11}$ and $3 \times 10^{11}$ particles, various plasma density gradients ($-20 ÷20\%$) and two plasma densities ($2\times 10^{14} \text{cm}^{-3}$ and $7 \times 10^{14} \text{cm}^{-3}$). The agreement is reached only in the case of a wide enough simulation box (at least five plasma wavelengths). △ Less

Submitted 26 August, 2020; originally announced August 2020.

Comments: 8 pages, 9 figures, 1 table

A route to improving RPA excitation energies through its connection to equation-of-motion coupled cluster theory

Authors: Varun Rishi, Ajith Perera, Rodney J. Bartlett

Abstract: We revisit the connection between equation-of-motion coupled cluster (EOM-CC) and random phase approximation (RPA) explored recently by Berkelbach [J. Chem. Phys. 149, 041103 (2018)] and unify various methodological aspects of these diverse treatment of ground and excited states. The identity of RPA and EOM-CC based on the ring coupled cluster doubles is established with numerical results which wa… ▽ More We revisit the connection between equation-of-motion coupled cluster (EOM-CC) and random phase approximation (RPA) explored recently by Berkelbach [J. Chem. Phys. 149, 041103 (2018)] and unify various methodological aspects of these diverse treatment of ground and excited states. The identity of RPA and EOM-CC based on the ring coupled cluster doubles is established with numerical results which was proved previously on theoretical grounds. We then introduce new approximations in EOM-CC and RPA family of methods, assess their numerical performance and explore a way to reap the benefits of such a connection to improve on excitation energies. Our results suggest that addition of perturbative corrections to account for double excitations and missing exchange effects could result in significantly improved estimates. △ Less

Submitted 6 November, 2020; v1 submitted 1 August, 2020; originally announced August 2020.

On the X-ray scattering pre-peak of linear mono-ols and the related micro-structure from computer simulations

Authors: Martina Pozar, Jennifer Bolle, Christian Sternemann, Aurélien Perera

Abstract: The X-ray scattering intensities I(k) of linear alkanols OH(CH2)n-1CH3, obtained from experiments (methanol to 1-undecanol) and computer simulations (methanol to 1-nonanol) of different force field models, are comparatively studied, particularly in order to explain the origin and the properties of the scattering pre-peak in the k-vector range 0.3A^{-1}-1A^{-1}. The experimental I(k) show two appar… ▽ More The X-ray scattering intensities I(k) of linear alkanols OH(CH2)n-1CH3, obtained from experiments (methanol to 1-undecanol) and computer simulations (methanol to 1-nonanol) of different force field models, are comparatively studied, particularly in order to explain the origin and the properties of the scattering pre-peak in the k-vector range 0.3A^{-1}-1A^{-1}. The experimental I(k) show two apparent features: the pre-peak position kP decreases with increasing n, and more intriguingly, the amplitude AP goes through a maximum at 1-butanol (n=4). The first feature is well reproduced by all force field models, while the second shows a strong model dependence. The simulations reveal various shapes of clusters of the hydroxyl head-group, from n>2. kP is directly related to the size of the \emph{meta-objects} corresponding to such clusters surrounded by their alkyl tails. The explanation of the Ap turnover at n=4 is more involved, in terms of cancellations of atom-atom S(k) contributions related to domain ordering. The flexibility of the alkyl tails tend to reduce the cross contributions, thus revealing the crucial importance of this parameter in the models. Force fields with all-atom representation are less successful in reproducing the pre-peak features for smaller alkanols n<6, possibly because they blur the charge ordering process since all atoms bear partial charges. The analysis clearly shows that it is not possible to obtain a model free explanation of the features of I(k) △ Less

Submitted 19 June, 2020; originally announced June 2020.

Comments: 23 pages, 15 figures

Visualization of radiotracers for SPECT imaging using a Timepix detector with a coded aperture

Authors: V. Rozhkov, G. Chelkov, I. Hernández, O. Ivanov, D. Kozhevniko, A. Leyva, A. Perera, D. Rastorguev, P. Smolyanskiy, L. Torres, A. Zhemchugov

Abstract: The work shows the ability to visualize radiotracers used in SPECT with a system based on a coded aperture mask and a hybrid pixel Timepix detector with the CdTe sensor. Characterization of the system using X-rays and radioactive sources confirms that the spatial resolution of less than 1 mm with a field of view 3 cm x 3 cm can be achieved. The results of a simulation study to determine the expect… ▽ More The work shows the ability to visualize radiotracers used in SPECT with a system based on a coded aperture mask and a hybrid pixel Timepix detector with the CdTe sensor. Characterization of the system using X-rays and radioactive sources confirms that the spatial resolution of less than 1 mm with a field of view 3 cm x 3 cm can be achieved. The results of a simulation study to determine the expected spatial resolution of the system in the focal plane for the various radionuclides is presented. The possibility of using this system with a thin (1.5 mm) coded aperture mask for reconstructing images of gamma emitters with the energy up to 180 keV is demonstrated. △ Less

Submitted 28 May, 2020; v1 submitted 20 April, 2020; originally announced April 2020.

A review of assessment methods for the urban environment and its energy sustainability to guarantee climate adaptation of future cities

Authors: Dasaraden Mauree, Emanuele Naboni, Silvia Coccolo, A. T. D. Perera, Vahid Nik, Jean-Louis Scartezzini

Abstract: The current climate change is calling for drastic reduction of energy demand as well as of greenhouse gases. Besides this, cities also need to adapt to face the challenges related to climate change. Cities, with their complex urban texture and fabric can be represented as a diverse ecosystem that do not have a clear and defined boundary. Multiple tools that have been developed, in the recent years… ▽ More The current climate change is calling for drastic reduction of energy demand as well as of greenhouse gases. Besides this, cities also need to adapt to face the challenges related to climate change. Cities, with their complex urban texture and fabric can be represented as a diverse ecosystem that do not have a clear and defined boundary. Multiple tools that have been developed, in the recent years, for assessment of urban climate, building energy demand, the outdoor thermal comfort and the energy systems. In this review, we, however, noted that these tools often address only one or two of these urban planning aspects. There is however an intricate link between them. For instance, the outdoor comfort assessment has showed that there is a strong link between biometeorology and architecture and urban climate. Additionally, to address the challenges of the energy transition, there will be a convergence of the energy needs in the future with an energy nexus regrouping the energy demand of urban areas. It is also highlighted that the uncertainty related to future climatic data makes urban adaptation and mitigation strategies complex to implement and to design given the lack of a comprehensive framework. We thus conclude by suggesting the need for a holistic interface to take into account this multi-dimensional problem. With the help of such a platform a positive loop in urban design can be initiated leading to the development of low carbon cities and/or with the use of blue and green infrastructure to have a positive impact on the mitigation and adaptation strategies. △ Less

Submitted 26 June, 2019; v1 submitted 14 June, 2019; originally announced June 2019.

Journal ref: Renewable and Sustainable Energy Reviews, 2019

Modeling micro-heterogeneity in mixtures: the role of many body terms

Authors: Anthony Baptista, Aurélien Perera

Abstract: A two-component interaction model is introduced herein, which allows to describe macroscopic miscibility with various modes of tunable micro-segregation, ranging from phase separation to micro-segregation, and in excellent agreement for structural quantities obtained from simulations and the liquid state hypernetted-chain like integral equation theory. The model is based on the conjecture that the… ▽ More A two-component interaction model is introduced herein, which allows to describe macroscopic miscibility with various modes of tunable micro-segregation, ranging from phase separation to micro-segregation, and in excellent agreement for structural quantities obtained from simulations and the liquid state hypernetted-chain like integral equation theory. The model is based on the conjecture that the many-body correlation bridge function term in the closure relation can be divided into one part representing the segregation effects, which are modeled herein, and the usual part representing random many body fluctuations. Furthermore, the model allows to fully neglect these second contributions, thus increasing the agreement between the simulations and the theory. The analysis of the retained part of the many body correlations gives important clues about how to model the many body bridge functions for more realistic systems exhibiting micro-segregation, such as aqueous mixtures. △ Less

Submitted 12 February, 2019; v1 submitted 16 October, 2018; originally announced October 2018.

Comments: 6 figures

Journal ref: J. Chem. Phys. 150, 000000 (2019)

Experimental observation of proton bunch modulation in a plasma, at varying plasma densities

Authors: E. Adli, A. Ahuja, O. Apsimon, R. Apsimon, A. -M. Bachmann, D. Barrientos, M. M. Barros, J. Batkiewicz, F. Batsch, J. Bauche, V. K. Berglyd Olsen, M. Bernardini, B. Biskup, A. Boccardi, T. Bogey, T. Bohl, C. Bracco, F. Braunmüller, S. Burger, G. Burt, S. Bustamante, B. Buttenschön, A. Caldwell, M. Cascella, J. Chappell , et al. (87 additional authors not shown)

Abstract: We give direct experimental evidence for the observation of the full transverse self-modulation of a relativistic proton bunch propagating through a dense plasma. The bunch exits the plasma with a density modulation resulting from radial wakefield effects with a period reciprocal to the plasma frequency. We show that the modulation is seeded by using an intense laser pulse co-propagating with the… ▽ More We give direct experimental evidence for the observation of the full transverse self-modulation of a relativistic proton bunch propagating through a dense plasma. The bunch exits the plasma with a density modulation resulting from radial wakefield effects with a period reciprocal to the plasma frequency. We show that the modulation is seeded by using an intense laser pulse co-propagating with the proton bunch which creates a relativistic ionization front within the bunch. We show by varying the plasma density over one order of magnitude that the modulation period scales with the expected dependence on the plasma density. △ Less

Submitted 1 April, 2019; v1 submitted 12 September, 2018; originally announced September 2018.

Comments: 4 figures, AWAKE collaboration paper, Submitted to PRL

Journal ref: Phys. Rev. Lett. 122, 054802 (2019)

Acceleration of electrons in the plasma wakefield of a proton bunch

Authors: The AWAKE Collaboration, E. Adli, A. Ahuja, O. Apsimon, R. Apsimon, A. -M. Bachmann, D. Barrientos, F. Batsch, J. Bauche, V. K. Berglyd Olsen, M. Bernardini, T. Bohl, C. Bracco, F. Braunmueller, G. Burt, B. Buttenschoen, A. Caldwell, M. Cascella, J. Chappell, E. Chevallay, M. Chung, D. Cooke, H. Damerau, L. Deacon, L. H. Deubner , et al. (69 additional authors not shown)

Abstract: High energy particle accelerators have been crucial in providing a deeper understanding of fundamental particles and the forces that govern their interactions. In order to increase the energy or reduce the size of the accelerator, new acceleration schemes need to be developed. Plasma wakefield acceleration, in which the electrons in a plasma are excited, leading to strong electric fields, is one s… ▽ More High energy particle accelerators have been crucial in providing a deeper understanding of fundamental particles and the forces that govern their interactions. In order to increase the energy or reduce the size of the accelerator, new acceleration schemes need to be developed. Plasma wakefield acceleration, in which the electrons in a plasma are excited, leading to strong electric fields, is one such promising novel acceleration technique. Pioneering experiments have shown that an intense laser pulse or electron bunch traversing a plasma, drives electric fields of 10s GV/m and above. These values are well beyond those achieved in conventional RF accelerators which are limited to ~0.1 GV/m. A limitation of laser pulses and electron bunches is their low stored energy, which motivates the use of multiple stages to reach very high energies. The use of proton bunches is compelling, as they have the potential to drive wakefields and accelerate electrons to high energy in a single accelerating stage. The long proton bunches currently available can be used, as they undergo self-modulation, a particle-plasma interaction which longitudinally splits the bunch into a series of high density microbunches, which then act resonantly to create large wakefields. The AWAKE experiment at CERN uses intense bunches of protons, each of energy 400 GeV, with a total bunch energy of 19 kJ, to drive a wakefield in a 10 m long plasma. Bunches of electrons are injected into the wakefield formed by the proton microbunches. This paper presents measurements of electrons accelerated up to 2 GeV at AWAKE. This constitutes the first demonstration of proton-driven plasma wakefield acceleration. The potential for this scheme to produce very high energy electron bunches in a single accelerating stage means that the results shown here are a significant step towards the development of future high energy particle accelerators. △ Less

Submitted 11 October, 2018; v1 submitted 29 August, 2018; originally announced August 2018.

Comments: 7 pages, 4 figures. Updated acknowledgements and one reference

A comparative study of aqueous DMSO mixtures by computer simulations and integral equation theories

Authors: Aurélien Perera, Bernarda Lovrinčević

Abstract: Several computer simulation studies of aqueous dimethylsulfoxyde with different force field models, and conducted by different authors, point out to an anomalous depressing of second and third neighbour correlations of the water-water radial distribution functions. This seemingly universal feature can be interpreted as the formation of linear water clusters. We test here the ability of liquid stat… ▽ More Several computer simulation studies of aqueous dimethylsulfoxyde with different force field models, and conducted by different authors, point out to an anomalous depressing of second and third neighbour correlations of the water-water radial distribution functions. This seemingly universal feature can be interpreted as the formation of linear water clusters. We test here the ability of liquid state integral equation theories to reproduce this feature. It is found that the incorporation of the water bridge diagram function is required to reproduce this feature. These theories are generally unable to properly reproduce atom-atom distribution functions. However, the near-ideal Kirkwood-Buff integrals are relatively well reproduced. We compute the Xray scattering function and compare with available experimental results, with the particular focus to explain why this data does not reproduce the cluster pre-peak observed in the water-water structure factor. △ Less

Submitted 4 January, 2018; originally announced January 2018.

Comments: 31 pages, 10 figures

Molecular emulsions: from charge order to domain order

Authors: Aurélien Perera

Abstract: Aqueous mixtures of small molecules, such as lower n-alkanols for example, are known to be micro-segregated, with domains in the nano-meter range. One consequence of micro-segregated domains would be the existence of long range domain-domain oscillatory correlations in the various atom- atom pair correlation functions, and subsequent pre-peaks in the corresponding atom atom structure factors, in t… ▽ More Aqueous mixtures of small molecules, such as lower n-alkanols for example, are known to be micro-segregated, with domains in the nano-meter range. One consequence of micro-segregated domains would be the existence of long range domain-domain oscillatory correlations in the various atom- atom pair correlation functions, and subsequent pre-peaks in the corresponding atom atom structure factors, in the q-vector range corresponding to nano-sized domains. However, no such pre-peak have ever been observed in the large corpus of radiation scattering data published so far. Here, through large scale simulations of aqueous-1propanol mixtures, I report that the domain pre-peak contributions in the atom-atom structure factors exactly cancel each other in the total scattering intensity, thus suppressing the pre-peak in agreement with the experimental findings. This cancellation is explained by drawing an analogy between the charge order found in ionic fluids and the segregated domain order. This finding opens new interpretation of the well known scattering pre-peak observed in micro-emulsions. In particular, it implies that scattering experiment cannot detect homogeneous domain segregation, hence cannot lead to a proper microscopic description of atom-atom correlations in domain ordered mixtures. △ Less

Submitted 28 July, 2017; originally announced July 2017.

Comments: 21 pages, 5 figures, research paper

Journal ref: Phys. Chem. Chem. Phys., 2017, 19, 28275

Predictive coupled-cluster isomer orderings for some Si${}_n$C${}_m$ ($m, n\le 12$) clusters; A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks

Authors: Jason N. Byrd, Jesse J. Lutz, Yifan Jin, Duminda S. Ranasinghe, John A. Montgomery Jr., Ajith Perera, Xiaofeng F. Duan, Larry W. Burggraf, Beverly A. Sanders, Rodney J. Bartlett

Abstract: The accurate determination of the preferred ${\rm Si}_{12}{\rm C}_{12}$ isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accur… ▽ More The accurate determination of the preferred ${\rm Si}_{12}{\rm C}_{12}$ isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC$_3$ to ${\rm Si}_{12}{\rm C}_{12}$. It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and CCSD extrapolation with triple-$ζ$ (T) correlation, the {\it closo} ${\rm Si}_{12}{\rm C}_{12}$ isomer is identified to be the preferred isomer in support of previous calculations [J. Chem. Phys. 2015, 142, 034303]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post MBPT(2) correlation energy is found to be an excellent balance between efficiency and accuracy. △ Less

Submitted 21 June, 2016; originally announced June 2016.

Approximating electronically excited states with equation-of-motion linear coupled-cluster theory

Authors: Jason N. Byrd, Varun Rishi, Ajith Perera, Rodney J. Bartlett

Abstract: A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Møller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory (EOM-MBPT(2)) equations and two new equation-of-motion methods based on the linear coupled-cluster doubles (EOM-LCCD)… ▽ More A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Møller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory (EOM-MBPT(2)) equations and two new equation-of-motion methods based on the linear coupled-cluster doubles (EOM-LCCD) and linear coupled-cluster singles and doubles (EOM-LCCSD) wavefunctions. This is achieved by performing a short-circuiting procedure on the MBPT(2) similarity transformed Hamiltonian. These new methods are benchmarked against very accurate theoretical and experimental spectra from 25 small organic molecules. It is found that the proposed methods have excellent agreement with canonical EOM-CCSD state for state orderings and relative excited state energies as well as acceptable quantitative agreement for absolute excitation energies compared with the best estimate theory and experimental spectra. △ Less

Submitted 7 July, 2015; originally announced July 2015.

Comments: 9 pages 3 figures

Apparent density fluctuations in N-constant ensemble simulations

Authors: Aurelien Perera, Franjo Sokolic, Larisa Zoranic

Abstract: In computer simulations performed in constant number of particles ensembles, although the total number of particles N contained in the simulation box does not fluctuate, hence giving a zero apparent compressibility, there are still local fluctuations in the number of particles. It is shown herein that these apparent fluctuations produce a compressibility that can be computed from the calculated… ▽ More In computer simulations performed in constant number of particles ensembles, although the total number of particles N contained in the simulation box does not fluctuate, hence giving a zero apparent compressibility, there are still local fluctuations in the number of particles. It is shown herein that these apparent fluctuations produce a compressibility that can be computed from the calculated radial distribution function, and which matches to a great accuracy the compressibility of the fluid for the open system. This statement implies that the radial distribution function evaluated in simulation of constant number of particles is identical to that evaluated in the grand canonical ensemble, for the entire distance range within half-box width. This is illustrated for the hard sphere and Lennard-Jones fluids and for molecular models of water. The origin of this apparent fluctuation is that the bulk of the remaining particles, outside the range over which the distribution function is calculated, act as a reservoir of particles for those within this range, thanks to the periodic boundary conditions. The implications on the calculation of the Kirkwood-Buff integrals are discussed. △ Less

Submitted 17 August, 2007; originally announced August 2007.

Comments: 15 pages, 5 figures

Microstructure of neat alcohols

Authors: Aurelien Perera, Franjo Sokolic, Larisa Zoranic

Abstract: Formation of microstructure in homogeneous associated liquids is analysed through the density-density pair correlation functions, both in direct and reciprocal space, as well as an effective local one-body density function. This is illustrated through a molecular dynamics study of two neat alcohols, namely methanol and \emph{tert}-butanol, which have a rich microstructure: chain-like molecular a… ▽ More Formation of microstructure in homogeneous associated liquids is analysed through the density-density pair correlation functions, both in direct and reciprocal space, as well as an effective local one-body density function. This is illustrated through a molecular dynamics study of two neat alcohols, namely methanol and \emph{tert}-butanol, which have a rich microstructure: chain-like molecular association for the former and micelle-like for the latter. The relation to hydrogen bonding interaction is demonstrated. The apparent failure to find microstructure in water -a stronger hydrogen bonding liquid- with the same tools, is discussed. △ Less

Submitted 28 March, 2007; originally announced March 2007.