On the Dynamics through a Conical Intersection.
Conical intersections represent critical topological features of potential energy surfaces and open ultrafast nonradiative deactivation channels for photoexcited molecules. In the following, we investigate how this funneling picture is transposed in the eyes of the exact factorization formalism for a 2D model system. The exact factorization of the total molecular wave function leads to the fundamental concept of time-dependent potential energy surface and time-dependent vector potential, whose behavior during a dynamics through a conical intersection has up to now remained unexplored. Despite the fact that these quantities might be viewed as time-dependent generalizations of the adiabatic potential energy surfaces and the nonadiabatic coupling vectors, characteristic quantities appearing in the Born-Oppenheimer framework, we observe that they do not exhibit particular topological features in the region of conical intersection but still reflect the complex dynamics of the nuclear wavepacket.
Centre for Computational Chemistry, School of Chemistry, University of Bristol , Bristol BS8 1TS, United Kingdom.
Basile F E
http://orcid.org/0000-0002-1705-473X
BF
Curchod
Laboratoire de Chimie Physique, UMR 8000 CNRS/University Paris-Sud, University Paris-Saclay , 91405 Orsay, France.
Federica
http://orcid.org/0000-0003-2951-4964
F
Agostini