Anomalous molecular dynamics in the vicinity of a conical intersection

¹ Department of Physics, Stockholm University - SE-106 91 Stockholm, Sweden, EU
² Institut für Theoretische Physik, Universität zu Köln - Köln, 50937, Germany, EU

Received: 7 November 2012
Accepted: 29 January 2013

Abstract

Conical intersections between molecular electronic potential energy surfaces can greatly affect molecular dynamics and chemical properties. Molecular gauge theory is capable of explaining many of these often unexpected phenomena deriving from the physics of the conical intersection. Here we will give an example of anomalous dynamics in the paradigm E × ϵ Jahn-Teller model, which does not allow for a simple explanation in terms of standard molecular gauge theory. By introducing a dual gauge theory, we unwind this surprising behavior by identifying it with an intrinsic spin Hall effect. Thus, this work link knowledge of condensed-matter theories with non-adiabatic molecular dynamics. Furthermore, via ab initio calculations of potential energy surfaces, the findings are as well demonstrated to appear in a realistic system such as the Li₃ molecule.