Simulating Vibronic Spectra without Born–Oppenheimer Surfaces
| Autor: | Aaron Kelly, Angel Rubio, Shunsuke A. Sato, Kevin Lively, Guillermo Albareda |
|---|---|
| Přispěvatelé: | European Commission |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Letter
molecular systems Born–Oppenheimer approximation FOS: Physical sciences Molecular systems 01 natural sciences 7. Clean energy quantum Franck-Condon effects benzene symbols.namesake Physics - Chemical Physics Quantum mechanics 0103 physical sciences Physics::Atomic and Molecular Clusters Vibronic spectroscopy General Materials Science Physical and Theoretical Chemistry Physics::Chemical Physics 010306 general physics Wave function linear vibronic spectra Chemical Physics (physics.chem-ph) Physics 010304 chemical physics single-trajectory Ehrenfest first-principles approaches Condensed Matter - Other Condensed Matter symbols H2 molecule Other Condensed Matter (cond-mat.other) |
| Zdroj: | The Journal of Physical Chemistry Letters Addi: Archivo Digital para la Docencia y la Investigación Universidad del País Vasco Addi. Archivo Digital para la Docencia y la Investigación instname |
| ISSN: | 1948-7185 |
| Popis: | 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-trajectory Ehrenfest dynamics. These results form the foundation for nonlinear spectral calculations and show promise for future application in capturing phenomena associated with vibronic coupling in more complex molecular and potentially condensed phase systems 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 Foundation |
| Databáze: | OpenAIRE |
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