Simulating Vibronic Spectra without Born-Oppenheimer Surfaces

TL;DR

This paper introduces a first-principles method to simulate vibronic spectra without explicit Born-Oppenheimer surfaces, accurately capturing vibronic structures and quantum effects in molecules like  and benzene.

Contribution

It presents a novel approach that bypasses the need for multiple potential energy surfaces, using mean field and beyond mean field dynamics for vibronic spectrum simulation.

Findings

Accurately reproduces vibronic structure in  molecule

Qualitative agreement with experimental benzene absorption spectrum

Demonstrates potential for complex molecular and condensed phase systems

Abstract

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.