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Nuclear–Electronic Orbital Quantum Mechanical/Molecular Mechanical Real-Time Dynamics

Journal Article · · Journal of Physical Chemistry Letters
 [1];  [2];  [2]
  1. Yale University, New Haven, CT (United States); Princeton University
  2. Yale University, New Haven, CT (United States)
+ Show Author Affiliations
Simulating the nuclear–electronic quantum dynamics of large-scale molecular systems in the condensed phase is key for studying biologically and chemically important processes such as proton transfer and proton-coupled electron transfer reactions. Herein, the real-time nuclear–electronic orbital time-dependent density functional theory (RT-NEO-TDDFT) approach is combined with a hybrid quantum mechanical/molecular mechanical (QM/MM) strategy to enable the accurate description of coupled nuclear–electronic quantum dynamics in the presence of heterogeneous environments such as solvent or proteins. The densities of the electrons and quantum protons are propagated in real time, while the other nuclei are propagated classically on the instantaneous electron–proton vibronic surface. This approach is applied to phenol bound to lysozyme, intramolecular proton transfer in malonaldehyde, and nonequilibrium excited-state intramolecular proton transfer in o-hydroxybenzaldehyde. Furthermore, these examples illustrate that the RT-NEO-TDDFT framework, coupled with an atomistic representation of the environment, allows the simulation of condensed-phase systems that exhibit significant nuclear quantum effects.
Research Organization:
Yale University, New Haven, CT (United States); University of Washington, Seattle, WA (United States)
Sponsoring Organization:
USDOE; National Science Foundation (NSF); National Institutes of Health (NIH)
Grant/Contract Number:
SC0023284
OSTI ID:
2554033
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 43 Vol. 14; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Computational chemistry
Electrical properties
QM/MM
Reaction mechanisms
Solvents