TY - JOUR
T1 - Direct Chemical Dynamics Simulations
AU - Pratihar, Subha
AU - Ma, Xinyou
AU - Homayoon, Zahra
AU - Barnes, George L.
AU - Hase, William L.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/15
Y1 - 2017/3/15
N2 - In a direct dynamics simulation, the technologies of chemical dynamics and electronic structure theory are coupled so that the potential energy, gradient, and Hessian required from the simulation are obtained directly from the electronic structure theory. These simulations are extensively used to (1) interpret experimental results and understand the atomic-level dynamics of chemical reactions; (2) illustrate the ability of classical simulations to correctly interpret and predict chemical dynamics when quantum effects are expected to be unimportant; (3) obtain the correct classical dynamics predicted by an electronic structure theory; (4) determine a deeper understanding of when statistical theories are valid for predicting the mechanisms and rates of chemical reactions; and (5) discover new reaction pathways and chemical dynamics. Direct dynamics simulation studies are described for bimolecular SN2 nucleophilic substitution, unimolecular decomposition, post-transition-state dynamics, mass spectrometry experiments, and semiclassical vibrational spectra. Also included are discussions of quantum effects, the accuracy of classical chemical dynamics simulation, and the methodology of direct dynamics.
AB - In a direct dynamics simulation, the technologies of chemical dynamics and electronic structure theory are coupled so that the potential energy, gradient, and Hessian required from the simulation are obtained directly from the electronic structure theory. These simulations are extensively used to (1) interpret experimental results and understand the atomic-level dynamics of chemical reactions; (2) illustrate the ability of classical simulations to correctly interpret and predict chemical dynamics when quantum effects are expected to be unimportant; (3) obtain the correct classical dynamics predicted by an electronic structure theory; (4) determine a deeper understanding of when statistical theories are valid for predicting the mechanisms and rates of chemical reactions; and (5) discover new reaction pathways and chemical dynamics. Direct dynamics simulation studies are described for bimolecular SN2 nucleophilic substitution, unimolecular decomposition, post-transition-state dynamics, mass spectrometry experiments, and semiclassical vibrational spectra. Also included are discussions of quantum effects, the accuracy of classical chemical dynamics simulation, and the methodology of direct dynamics.
UR - http://www.scopus.com/inward/record.url?scp=85015254040&partnerID=8YFLogxK
U2 - 10.1021/jacs.6b12017
DO - 10.1021/jacs.6b12017
M3 - Article
C2 - 28118543
AN - SCOPUS:85015254040
SN - 0002-7863
VL - 139
SP - 3570
EP - 3590
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 10
ER -