Applicability of the Thawed Gaussian Wavepacket Dynamics to the Calculation of Vibronic Spectra of Molecules with Double-Well Potential Energy Surfaces.

@article{Begui2022ApplicabilityOT,
  title={Applicability of the Thawed Gaussian Wavepacket Dynamics to the Calculation of Vibronic Spectra of Molecules with Double-Well Potential Energy Surfaces.},
  author={Tomislav Begu{\vs}i{\'c} and Enrico Tapavicza and Jiř{\'i} Van{\'i}{\vc}ek},
  journal={Journal of chemical theory and computation},
  year={2022}
}
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 limitations of the recently proposed single-Hessian thawed Gaussian approximation for the simulation of spectra of systems with double-well potentials, including 1,2,4,5-tetrafluorobenzene, ammonia, phosphine, and arsine. This semiclassical wavepacket approach is… 
1 Citations

Figures from this paper

On the Importance of Well-Defined Thermal Correlation Functions in Simulating Vibronic Spectra.
Two difficulties associated with the computations of thermal vibrational correlation functions are discussed. The first one is the lack of a well-behaved expression that is valid at both

References

SHOWING 1-10 OF 103 REFERENCES
Unsupervised Machine Learning Neural Gas Algorithm for Accurate Evaluations of the Hessian Matrix in Molecular Dynamics
TLDR
The algorithm belongs to the family of unsupervised machine learning methods, and it is based on the neural gas idea, where neurons are molecular configurations whose Hessians are adopted for groups of molecular dynamics configurations with similar geometries.
Optimal Representation of the Nuclear Ensemble: Application to Electronic Spectroscopy.
TLDR
This work addresses the question of how many configurations do the authors need and how to select them most efficiently in the context of electronic spectroscopy, and proposes a representative sampling technique that allows for a dramatic reduction of the sample size.
Computational molecular spectroscopy
TLDR
The Primer provides essential information about the characteristics, accuracy and limitations of current computational approaches used for modelling spectroscopic phenomena with a focus on estimating error bars, limitations and coupling interpretability to accuracy.
Efficient Semiclassical Dynamics for Vibronic Spectroscopy beyond Harmonic, Condon, and Zero-Temperature Approximations.
TLDR
This work shows how the on-the-fly ab initio thawed Gaussian approximation, which partially includes anharmonicity effects, can be combined with the thermo-field dynamics to treat non-zero temperature and with the Herzberg-Teller correction to include non-Condon effects.
Finite-Temperature, Anharmonicity, and Duschinsky Effects on the Two-Dimensional Electronic Spectra from Ab Initio Thermo-Field Gaussian Wavepacket Dynamics
TLDR
An efficient method for computing finite-temperature two-dimensional spectra is obtained by combining the exact thermo-field dynamics approach with the thawed Gaussian approximation for the wavepacket dynamics, which is exact for any displaced, distorted, and Duschinsky-rotated harmonic potential but also accounts partially for anharmonicity effects in general potentials.
Explicit environmental and vibronic effects in simulations of linear and nonlinear optical spectroscopy.
TLDR
Three approaches of varying computational cost are presented for combining ensemble sampling of chromophore-environment configurations with Franck-Condon line shapes for simulating linear spectra and two analogous approaches for nonlinear spectra.
First principles theoretical spectroscopy of methylene blue: Between limitations of time-dependent density functional theory approximations and its realistic description in the solvent.
TLDR
TDDFT with a non-empirical optimally tuned range-separated hybrid functional is used to explore the optical excitations of gas phase and solvated methylene blue and rationalize and validate that by extrapolating the optimized range separation parameter to an infinite amount of solvating molecules, the optical gap of methyleneblue is well described.
Vibronic and Environmental Effects in Simulations of Optical Spectroscopy.
TLDR
Two approaches that consider both the explicit atomistic environment and the vibronic transitions are outlined that show significant potential for making strides toward more accurate optical spectroscopy simulations of complex condensed phase systems.
Coherent state based solutions of the time-dependent Schrödinger equation: hierarchy of approximations to the variational principle
In this review, we give a comprehensive comparison of the most widely used coherent state (CS) based methods to solve the time-dependent Schrödinger equation (TDSE). Starting from the fully
The limits of nuclear ensemble method for electronic spectra simulations: Temperature dependence of the (E)-azobenzene spectrum.
TLDR
It is shown that the nuclear ensemble method based on the path integral molecular dynamics combined with range-separated hybrid functionals provides quantitatively accurate spectra and their differences and that hundreds of thousands of samples are necessary for the unambiguous explanation of the observed temperature effects.
...
...