Simulating Vibronic Spectra without Born-Oppenheimer Surfaces.

ABSTRACT: We show how linear vibronic spectra in molecular systems can be simulated efficiently using first-principles approaches without relying on the explicit use of multiple Born-Oppenheimer potential energy surfaces. We demonstrate and analyze the performance of mean-field and beyond-mean-field dynamics techniques for the H₂ molecule in one dimension, in the later case capturing the vibronic structure quite accurately, including quantum Franck-Condon effects. In a practical application of this methodology we simulate the absorption spectrum of benzene in full dimensionality using time-dependent density functional theory at the multitrajectory Ehrenfest level, finding good qualitative agreement with experiment and significant spectral reweighting compared to commonly used single-traje

SUBMITTER: Lively K 

PROVIDER: S-EPMC8020382 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature