Related papers: On-the-fly ab initio semiclassical evaluation of a…
Evaluation of symmetry-forbidden or weakly-allowed vibronic spectra requires treating the transition dipole moment beyond the Condon approximation. To include vibronic spectral features not captured in the global harmonic models, we have…
To compute and analyze vibrationally resolved electronic spectra at zero temperature, we have recently implemented the on-the-fly ab initio extended thawed Gaussian approximation [A. Patoz et al., J. Phys. Chem. Lett. 9, 2367 (2018)], which…
We present a methodology for computing vibrationally and time-resolved pump-probe spectra, which takes into account all vibrational degrees of freedom and is based on the combination of the thawed Gaussian approximation with on-the-fly ab…
We present a theory of electronic excitation energies and optical absorption spectra which incorporates energy-level renormalization and phonon-assisted optical absorption within a unified framework. Using time-independent perturbation…
Ab initio computation of two-dimensional electronic spectra is an expanding field, whose goal is improving upon simple, few-dimensional models often employed to explain experiments. Here, we propose an accurate and computationally…
Despite its simplicity, the single-trajectory thawed Gaussian approximation has proven useful for calculating vibrationally resolved electronic spectra of molecules with weakly anharmonic potential energy surfaces. Here, we show that the…
Simulating vibrationally resolved electronic spectra of anharmonic systems, especially those involving double-well potential energy surfaces, often requires expensive quantum dynamics methods. Here, we explore the applicability and…
We quantify the non-adiabatic contributions to the vibronic sidebands of equilibrium and explicitly time-resolved non-equilibrium photoelectron spectra for a vibronic model system of Trans-Polyacetylene. Using exact diagonalization, we…
Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better…
While dark transitions made bright by molecular motions determine the optoelectronic properties of many materials, simulating such non-Condon effects in condensed-phase spectroscopy remains a fundamental challenge. We derive a Gaussian…
The absorption spectrum of CO$_2$ in the wavelength range 120\,nm --- 160\,nm is analyzed by means of quantum mechanical calculations performed using vibronically coupled PESs of five singlet valence electronic states and the coordinate…
To alleviate the computational cost associated with on-the-fly ab initio semiclassical calculations of molecular spectra, we propose the single-Hessian thawed Gaussian approximation, in which the Hessian of the potential energy at all…
The coupling of atomic vibrations to electronic excitations - traditionally understood to be a source of energy loss in semiconductors - has recently been explored in photosynthetic light harvesting as a means to circumvent dissipation by…
We present an experimental and computational study of the nonlinear optical response of conduction electrons to intense terahertz (THz) electric field. Our observations (saturable absorption and an amplitude-dependent group refractive…
The renormalization of electronic eigenenergies due to electron-phonon coupling is sizable in many materials with light atoms. This effect, often neglected in ab-initio calculations, can be computed using the perturbation-based…
We study the absorption spectrum for a strongly degenerate Fermi gas confined in a harmonic trap. The spectrum is calculated using both the exact summation and also the Thomas-Fermi (TF) approximation. In the latter case, relatively simple…
We combine the semiclassical Herman--Kluk approximation with the coherence thermofield dynamics in order to evaluate vibrationally resolved electronic spectra at nonzero temperatures. In coherence thermofield dynamics, the dipole time…
Hagedorn wavepackets have been used to compute single vibronic level (SVL) spectra efficiently in model harmonic potentials. To make the Hagedorn approach practical for realistic polyatomic molecules with anharmonicity, here we combine…
We derive a Hierarchical Equations of Motion (HEOM) description of nonadiabatic Herzberg-Teller type coupling effects and of non-Condon effects in a system of electronic transitions interacting with intra- and inter-molecular vibrational…
Coherent multidimensional spectroscopy enables detailed investigations of vibronic effects in molecular and solid-state systems. We present explicit analytical expressions for multidimensional nonlinear response functions in the presence of…