When the Exact Factorization Meets Conical Intersections..

Agostini, Federica; Curchod, Basile F.E.

doi:10.1140/epjb/e2018-90117-6

When the Exact Factorization Meets Conical Intersections..

Agostini, Federica; Curchod, Basile F.E.

Authors

Federica Agostini

Dr Basile Curchod basile.f.curchod@durham.ac.uk
Academic Visitor

Abstract

Capturing nuclear dynamics through conical intersections is pivotal to understand the fate of photoexcited molecules. The concept of a conical intersection, however, belongs to a specific definition of the electronic states, within a Born–Huang representation of the molecular wavefunction. How would these ultrafast funneling processes be translated if an exact factorization of the molecular wavefunction were to be used? In this article, we build upon our recent analysis [B.F.E. Curchod, F. Agostini, J. Phys. Chem. Lett. 8, 831 (2017)] and address this question in a broader perspective by studying the dynamics of a nuclear wavepacket through two types of conical intersections, differing by the strength of their underlying diabatic coupling. Our results generalize our previous findings by (i) showing that the time-dependent potential energy surface smoothly varies, both in time and in position, between the corresponding diabatic and adiabatic potentials, with sometimes more complex features if interferences are observed, (ii) highlighting the non-trivial behavior of the time-dependent vector potential and the fact that it cannot be gauged away in general, and (iii) justifying some approximations employed in the derivation of a mixed quantum/classical scheme based on the exact factorization.

Citation

Agostini, F., & Curchod, B. F. (2018). When the Exact Factorization Meets Conical Intersections.. The European Physical Journal B, 91(7), Article 141. https://doi.org/10.1140/epjb/e2018-90117-6

Journal Article Type	Article
Acceptance Date	May 14, 2018
Online Publication Date	Jul 2, 2018
Publication Date	Jul 2, 2018
Deposit Date	May 15, 2018
Publicly Available Date	May 15, 2018
Journal	The European Physical Journal B
Print ISSN	1434-6028
Electronic ISSN	1434-6036
Publisher	SpringerOpen
Peer Reviewed	Peer Reviewed
Volume	91
Issue	7
Article Number	141
DOI	https://doi.org/10.1140/epjb/e2018-90117-6

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Copyright Statement
© The Author(s) 2018 Open Access This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.