Real-Time Time-Dependent Nuclear−Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation
- 6 April 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry Letters
- Vol. 11 (10), 4052-4058
- https://doi.org/10.1021/acs.jpclett.0c00701
Abstract
The quantum mechanical treatment of both electrons and nuclei is crucial in nonadiabatic 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 show 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 field, 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 dynamical processes within a time-dependent variational description for the coupled electronic and nuclear degrees of freedom.Keywords
Funding Information
- University of Washington
- Basic Energy Sciences (DE-SC0006863)
This publication has 51 references indexed in Scilit:
- Can Quantized Vibrational Effects Be Obtained from Ehrenfest Mixed Quantum-Classical Dynamics?The Journal of Physical Chemistry Letters, 2016
- Understanding the Surface Hopping View of Electronic Transitions and DecoherenceAnnual Review of Physical Chemistry, 2016
- Ab initio two-component Ehrenfest dynamicsThe Journal of Chemical Physics, 2015
- Modified Ehrenfest Formalism for Efficient Large-Scale ab initio Molecular DynamicsJournal of Chemical Theory and Computation, 2009
- Time-dependent density functional theory Ehrenfest dynamics: Collisions between atomic oxygen and graphite clustersThe Journal of Chemical Physics, 2007
- Ab initioEhrenfest dynamicsThe Journal of Chemical Physics, 2005
- Proton transfer in solution: Molecular dynamics with quantum transitionsThe Journal of Chemical Physics, 1994
- Molecular dynamics with electronic transitionsThe Journal of Chemical Physics, 1990
- The mean-field theory of nuclear structure and dynamicsReviews of Modern Physics, 1982
- Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H+ with D2The Journal of Chemical Physics, 1971