Skip to main content

Research Repository

Advanced Search

A walk through the approximations of ab initio multiple spawning

Mignolet, Benoit; Curchod, Basile F.E.

A walk through the approximations of ab initio multiple spawning Thumbnail


Authors

Benoit Mignolet



Abstract

Full multiple spawning offers an in principle exact framework for excited-state dynamics, where nuclear wavefunctions in different electronic states are represented by a set of coupled trajectory basis functions that follow classical trajectories. The couplings between trajectory basis functions can be approximated to treat molecular systems, leading to the ab initio multiple spawning method which has been successfully employed to study the photochemistry and photophysics of several molecules. However, a detailed investigation of its approximations and their consequences is currently missing in the literature. In this work, we simulate the explicit photoexcitation and subsequent excited-state dynamics of a simple system, LiH, and we analyze (i) the effect of the ab initio multiple spawning approximations on different observables and (ii) the convergence of the ab initio multiple spawning results towards numerically exact quantum dynamics upon a progressive relaxation of these approximations. We show that, despite the crude character of the approximations underlying ab initio multiple spawning for this low-dimensional system, the qualitative excited-state dynamics is adequately captured, and affordable corrections can further be applied to ameliorate the coupling between trajectory basis functions.

Citation

Mignolet, B., & Curchod, B. F. (2018). A walk through the approximations of ab initio multiple spawning. The Journal of Chemical Physics, 148(13), Article 134110. https://doi.org/10.1063/1.5022877

Journal Article Type Article
Acceptance Date Mar 8, 2018
Online Publication Date Apr 3, 2018
Publication Date Apr 3, 2018
Deposit Date Apr 5, 2018
Publicly Available Date Apr 3, 2019
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 148
Issue 13
Article Number 134110
DOI https://doi.org/10.1063/1.5022877

Files

Published Journal Article (2.6 Mb)
PDF

Copyright Statement
© 2018 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Mignolet, Benoit & Curchod, Basile F. E. (2018). A walk through the approximations of ab initio multiple spawning. The Journal of Chemical Physics 148(13): 134110 and may be found at https://doi.org/10.1063/1.5022877





You might also like



Downloadable Citations