The Damped Ehrenfest (D-Eh) method: Application to non-adiabatic reaction paths
File(s)1-s2.0-S2210271X19300441-main.pdf (2.44 MB)
Published version
Author(s)
Robb, Michael
Jenkins, Andrew J
Type
Journal Article
Abstract
An implementation of the Ehrenfest method with damped velocity is discussed. The method is then applied to study the non-adiabatic reaction paths for two simple chemical systems: the isomerization of the allene radical cation in its excited state and the channel 3 photochemical transformation of benzene to benzvalene. For both systems the initial conditions for the Ehrenfest trajectory were either an adiabatic eigenstate with the geometry close to a conical intersection, or a superposition of eigenstates at the geometry close to a conical intersection. In allene we were able to show that the adiabatic reaction, which passes through a conical intersection, stimulates electron dynamics. In benzene we were able to show the importance of the phase at the conical intersection for the generation of the benzevalene intermediate.
Date Issued
2019-03-15
Date Acceptance
2019-02-07
Citation
Computational and Theoretical Chemistry, 2019, 1152, pp.53-61
ISSN
0166-1280
Publisher
Elsevier
Start Page
53
End Page
61
Journal / Book Title
Computational and Theoretical Chemistry
Volume
1152
Copyright Statement
© 2019 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
(http://creativecommons.org/licenses/BY/4.0/).
Subjects
0306 Physical Chemistry (Incl. Structural)
0307 Theoretical And Computational Chemistry
Publication Status
Published
Date Publish Online
2019-02-08