When the Exact Factorization Meets Conical Intersections..

Agostini, Federica; Curchod, Basile F.E.

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
• Public URL: https://durham-repository.worktribe.com/output/1326703