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

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [2];  [1];  [2];  [1]
  1. Univ. of Washington, Seattle, WA (United States)
  2. Yale Univ., New Haven, CT (United States)
+ Show Author Affiliations
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.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Interfacial Dynamics in Radioactive Environments and Materials (IDREAM); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830; SC0006863
OSTI ID:
1763034
Report Number(s):
PNNL-SA--152537
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 10 Vol. 11; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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