Real-Time Time-Dependent Nuclear–Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation

Zhao, Luning; Tao, Zhen; Pavošević, Fabijan; Wildman, Andrew; Hammes-Schiffer, Sharon; Li, Xiaosong

doi:10.1021/acs.jpclett.0c00701

Title: Real-Time Time-Dependent Nuclear–Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation

Journal Article · Mon Apr 06 00:00:00 EDT 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c00701· OSTI ID:1763034

^[1]; Tao, Zhen ^[2]; Pavošević, Fabijan ^[2];

^[1];

^[2];

^[1]

Univ. of Washington, Seattle, WA (United States)
Yale Univ., New Haven, CT (United States)

The quantum mechanical treatment of both electrons and nuclei is crucial in nona- diabatic dynamical processes such as proton-coupled electron transfer. The nuclear electronic orbital (NEO) method provides an elegant framework for including nuclear quantum effects beyond the Born-Oppenheimer approximation. To enable the study of nonequilibrium properties, we derive and implement a real-time NEO (RT-NEO) approach based on time-dependent Hatree-Fock or density functional theory, in which both the electronic and nuclear degrees of freedom are propagated in a time-dependent variational framework. Nuclear and electronic spectral features can be resolved from the time-dependent dipole moment computed using the RT-NEO method. The test cases demonstrate the dynamical interplay between the quantum nuclei and the electrons through vibronic coupling. Moreover, vibrational excitation in the RT-NEO approach is demonstrated by applying a resonant driving eld, and electronic excitation is demonstrated by simulating excited state intramolecular proton transfer. This work shows that the RT-NEO approach is a promising tool to study nonadiabatic quantum dynamical processes within a time-dependent variational description for the coupled electronic and nuclear degrees of freedom.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; SC0006863; CHE-1762018

OSTI ID:: 1763034

Report Number(s):: PNNL-SA-152537

Journal Information:: Journal of Physical Chemistry Letters, Vol. 11, Issue 10; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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