Direct methods for non-adiabatic dynamics: connecting the single-set variational multi-confguration Gaussian (vMCG) and Ehrenfest perspectives
File(s)
Published version
Accepted version
Author(s)
Vacher, M
Bearpark, MJ
Robb, MA
Type
Journal Article
Abstract
In this article, we outline the current state-of-theart
“on-the-fly” methods for non-adiabatic dynamics, highlighting
the similarities and differences between them. We
derive the equations of motion for both the Ehrenfest and
variational multi-configuration Gaussian (vMCG) methods
from the Dirac–Frenkel variational principle. We explore
the connections between these two methods by presenting
an alternative derivation of the vMCG method, which gives
the Ehrenfest equations of motion when taking the appropriate
limits.
“on-the-fly” methods for non-adiabatic dynamics, highlighting
the similarities and differences between them. We
derive the equations of motion for both the Ehrenfest and
variational multi-configuration Gaussian (vMCG) methods
from the Dirac–Frenkel variational principle. We explore
the connections between these two methods by presenting
an alternative derivation of the vMCG method, which gives
the Ehrenfest equations of motion when taking the appropriate
limits.
Date Issued
2016-07-12
Date Acceptance
2016-06-20
Citation
Theoretical Chemistry Accounts, 2016, 135
ISSN
1432-881X
Publisher
Springer Verlag
Journal / Book Title
Theoretical Chemistry Accounts
Volume
135
Copyright Statement
© The Author(s) 2016. This article is published with open access at Springerlink.com
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/I032517/1
Subjects
Chemical Physics
0307 Theoretical And Computational Chemistry
Publication Status
Published
Article Number
187