Simulating Vibronic Spectra without Born-Oppenheimer Surfaces

Journal Of Physical Chemistry Letters 12,12, 3074 - 3081 (2021)

Simulating Vibronic Spectra without Born-Oppenheimer Surfaces

Kevin Lively, Guillermo Albareda, Shunsuke A. Sato, Aaron Kelly, Angel Rubio

We show how vibronic spectra in molecular systems can be simulated in an efficient and accurate way using first principles approaches without relying on the explicit use of multiple Born-Oppenheimer potential energy surfaces. We demonstrate and analyse the performance of mean field and beyond mean field dynamics techniques for the \ch{H_2} 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 multi-trajectory mean-field level, finding good qualitative agreement with experiment. These results show promise for future applications of this methodology in capturing phenomena associated with vibronic coupling in more complex molecular, and potentially condensed phase systems.

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This work was supported by the European Research Council (ERC-2015-AdG694097), the Cluster of Excellence Advanced Imaging of Matter’ (AIM), JSPS KAKENHI Grant Number 20K14382, Grupos Consolidados (IT1249-19) and SFB925. The Flatiron Institute is a division of the Simons Found

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