Competing quantum effects in heavy-atom tunnelling through conical intersections.

ABSTRACT: Thermally activated chemical reactions are typically understood in terms of overcoming potential-energy barriers. However, standard rate theories break down in the presence of a conical intersection (CI) because these processes are inherently nonadiabatic, invalidating the Born-Oppenheimer approximation. Moreover, CIs give rise to intricate nuclear quantum effects such as tunnelling and the geometric phase, which are neglected by standard trajectory-based simulations and remain largely unexplored in complex molecular systems. We present new semiclassical transition-state theories based on an extension of golden-rule instanton theory to describe nonadiabatic tunnelling through CIs and thus provide an intuitive picture for the reaction mechanism. We apply the method in conjunction with first

SUBMITTER: Fang W 

PROVIDER: S-EPMC10566476 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature