Simulating Vibronic Spectra without Born–Oppenheimer Surfaces

Lively, K.; Albareda Piquer, G.; Sato, S.; Kelly, A.; Rubio, A.

doi:10.1021/acs.jpclett.1c00073

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Simulating Vibronic Spectra without Born–Oppenheimer Surfaces

MPS-Authors

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Lively, K.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science;

/persons/resource/persons226200

Albareda Piquer, G.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science;
Institute of Theoretical and Computational Chemistry, University of Barcelona;
Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco;

/persons/resource/persons222317

Sato, S.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science;
Center for Computational Sciences, University of Tsukuba;

/persons/resource/persons196584

Kelly, A.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science;
Department of Chemistry, Dalhousie University;

/persons/resource/persons22028

Rubio, A.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science;
Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco;
Center for Computational Quantum Physics (CCQ), Flatiron Institute;

External Resource

https://dx.doi.org/10.1021/acs.jpclett.1c00073
(Publisher version)

https://arxiv.org/abs/2101.03007
(Preprint)

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acs.jpclett.1c00073.pdf
(Publisher version), 2MB

Supplementary Material (public)

jz1c00073_si_001.pdf
(Supplementary material), 558KB

Citation

Lively, K., Albareda Piquer, G., Sato, S., Kelly, A., & Rubio, A. (2021). Simulating Vibronic Spectra without Born–Oppenheimer Surfaces. The Journal of Physical Chemistry Letters, 12(12), 3074-3081. doi:10.1021/acs.jpclett.1c00073.

Cite as: https://hdl.handle.net/21.11116/0000-0008-6D29-1

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-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.