Broadband ultrafast self-heterodyned chiro-optical spectroscopy
Authors:
Francesco Gucci†,
Andrea Iudica†,
Andres Valladares Y Tacchi†,
Andrea Schirato,
Giulia Crotti,
Ryeong Myeong Kim,
Soo Min Lee,
Jeong Hyun Han,
Andrea Villa,
Dawar Ali,
Aurora Rizzo,
Margherita Maiuri,
Ki Tae Nam,
Giuseppe Della Valle,
Giulio Cerullo
Abstract:
Ultrafast chiro-optical spectroscopy provides unique access to the structural dynamics of molecules, spin-valley relaxation in semiconductors, and the non-equilibrium optical response of chiral nanophotonic systems. Yet, because chiral signals are intrinsically weak and time-resolved spectroscopy probes small photoinduced changes, transient chiro-optical responses are often difficult to isolate fr…
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Ultrafast chiro-optical spectroscopy provides unique access to the structural dynamics of molecules, spin-valley relaxation in semiconductors, and the non-equilibrium optical response of chiral nanophotonic systems. Yet, because chiral signals are intrinsically weak and time-resolved spectroscopy probes small photoinduced changes, transient chiro-optical responses are often difficult to isolate from parasitic achiral contributions. Here, we introduce a broadband ultrafast chiro-optical spectroscopy technique that integrates a birefringent common-path interferometer with an optical polarization bridge to sensitively detect photoinduced changes in the polarization state of light. Phase-sensitive self-heterodyned detection enables simultaneous measurement of transient circular dichroism and optical rotatory dispersion across a broad spectral range with ultrafast temporal resolution. Balanced detection suppresses excess laser noise, enabling exceptional sensitivity (<50 $μ$deg) close to shot-noise limit. We demonstrate this approach on an array of gold nano-helicoids, supported by a full-wave time-resolved model of the spatiotemporal dynamics of plasmonic non-equilibrium carriers and their associated optical nonlinearities. The model traces the system's transient chiro-optical response back to photoinduced modulations of the electric-magnetic dipole interaction in the nano-helicoid, elucidating the connection of near- and far-field dynamics in the non-equilibrium regime. We further investigate spin excitation, thermalization, and relaxation in a lead halide perovskite, establishing a novel approach to broadband time-resolved Faraday rotation. The simplicity, sensitivity, and wide applicability of this detection scheme provide a powerful platform for broadband ultrafast chiro-optical spectroscopy, opening new opportunities in biochemistry, solid-state physics, and nanophotonics.
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Submitted 13 November, 2025;
originally announced November 2025.
Hyperfine structure of Sc@C82 from ESR and DFT
Authors:
G. W. Morley,
B. J. Herbert,
S. M. Lee,
K. Porfyrakis,
T. J. S. Dennis,
D. Nguyen-Manh,
R. Scipioni,
J. van Tol,
A. P. Horsfield,
A. Ardavan,
D. G. Pettifor,
J. C. Green,
G. A. D. Briggs
Abstract:
The electron spin g- and hyperfine tensors of the endohedral metallofullerene Sc@C82 are anisotropic. Using electron spin resonance (ESR) and density functional theory (DFT), we can relate their principal axes to the coordinate frame of the molecule, finding that the g-tensor is not axially symmetric. The Sc bond with the cage is partly covalent and partly ionic. Most of the electron spin densit…
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The electron spin g- and hyperfine tensors of the endohedral metallofullerene Sc@C82 are anisotropic. Using electron spin resonance (ESR) and density functional theory (DFT), we can relate their principal axes to the coordinate frame of the molecule, finding that the g-tensor is not axially symmetric. The Sc bond with the cage is partly covalent and partly ionic. Most of the electron spin density is distributed around the carbon cage, but 5% is associated with the scandium d_yz orbital, and this drives the observed anisotropy.
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Submitted 11 September, 2008;
originally announced September 2008.
Anisotropic magnetization and sign change of dynamic susceptibility in Na0.85CoO2 single crystal
Authors:
J. S. Rhyee,
J. B. Peng,
C. T. Lin,
S. M. Lee
Abstract:
The DC and AC magnetic susceptibilities of Na0.85CoO2 single crystals were measured for the different crystal orientations of H//(ab)- and H//(c)-axis. The DC-magnetic susceptibility for H//(c)-direction exhibited the antiferromagnetic transition at TN= 22 K. The thermal hysteresis between the zero-field-cooled (ZFC) and the field-cooled (FC) magnetization below TN and the large frustration para…
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The DC and AC magnetic susceptibilities of Na0.85CoO2 single crystals were measured for the different crystal orientations of H//(ab)- and H//(c)-axis. The DC-magnetic susceptibility for H//(c)-direction exhibited the antiferromagnetic transition at TN= 22 K. The thermal hysteresis between the zero-field-cooled (ZFC) and the field-cooled (FC) magnetization below TN and the large frustration parameter indicated the spin frustration along the (c)-axis. For an applied magnetic field in H//(ab)-plane, the DC magnetic susceptibility exhibited the logarithmic divergent behavior at low temperatures (T < 6.8 K). This could be understood by the impurity spin effect, dressed by the spin fluctuation. From the AC magnetic susceptibility measurements, the real part of the AC-susceptibility for H//(ab) exhibited the spin glass-like behavior at low temperatures (T < 4 K). Remarkably, for an applied AC magnetic field with H//(c)-axis, the sign of the AC magnetic susceptibility changed from a positive to a negative value with increasing AC magnetic field frequency (f > 3 kHz) at low temperatures (T > 7 K). We interpret the sign change of AC magnetic susceptibility along the (c)-axis in terms of the sudden sign reversal of the phase difference from in-phase to out-of-phase response with an applied AC magnetic field in the AC-susceptibility phase space.
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Submitted 29 April, 2008;
originally announced April 2008.