Single-Hessian thawed Gaussian approximation

Tomislav Begušić

doi:10.1063/1.5090122

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Single-Hessian thawed Gaussian approximation

2019-04-19

Tomislav Begušić *

Manuel Cordova

Jiří Vaníček

DOI：10.1063/1.5090122

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Abstract

En 中文

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 points along an an harmonic classical trajectory is approximated by a constant matrix. The spectra obtained with this approximation are compared with the exact quantum spectra of a one-dimensional Morse potential and with the experimental spectra of ammonia and quinquethiophene. In all cases, the single Hessian version performs almost as well as the much more expensive on ab initio thawed Gaussian approximation and significantly better than the global harmonic schemes. Remarkably, unlike the thawed Gaussian approximation, the proposed method conserves energy exactly, despite the time dependence of the corresponding effective Hamiltonian, and, in addition, can be mapped to a higher-dimensional time independent classical Hamiltonian system. We also provide a detailed comparison with several related approximations used for accelerating prefactor calculations in semiclassical simulations. (C) 2019 Author(s).

Keywords:

TIME-DEPENDENT APPROACH

CLASSICAL S-MATRIX

HERZBERG-TELLER

FRANCK-CONDON

PHOTOELECTRON-SPECTRA

DYNAMICS SIMULATIONS

QUANTUM DYNAMICS

OPTICAL-SPECTRA

ABSORPTION

MOLECULES

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