skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ab Initio Nonadiabatic Quantum Molecular Dynamics

Abstract

Here, the Born–Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born–Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump–probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third classmore » of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Durham Univ., Durhmam (United Kingdom)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1471080
Grant/Contract Number:  
701355; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Volume: 118; Journal Issue: 7; Journal ID: ISSN 0009-2665
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Curchod, Basile F. E., and Martínez, Todd J. Ab Initio Nonadiabatic Quantum Molecular Dynamics. United States: N. p., 2018. Web. doi:10.1021/acs.chemrev.7b00423.
Curchod, Basile F. E., & Martínez, Todd J. Ab Initio Nonadiabatic Quantum Molecular Dynamics. United States. doi:10.1021/acs.chemrev.7b00423.
Curchod, Basile F. E., and Martínez, Todd J. Wed . "Ab Initio Nonadiabatic Quantum Molecular Dynamics". United States. doi:10.1021/acs.chemrev.7b00423. https://www.osti.gov/servlets/purl/1471080.
@article{osti_1471080,
title = {Ab Initio Nonadiabatic Quantum Molecular Dynamics},
author = {Curchod, Basile F. E. and Martínez, Todd J.},
abstractNote = {Here, the Born–Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born–Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump–probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.},
doi = {10.1021/acs.chemrev.7b00423},
journal = {Chemical Reviews},
number = 7,
volume = 118,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

Save / Share: