Limbu Dil K, Shakib Farnaz A
Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, New Jersey 07102, United States.
J Phys Chem Lett. 2023 Sep 28;14(38):8658-8666. doi: 10.1021/acs.jpclett.3c02085. Epub 2023 Sep 21.
Ring polymer surface hopping (RPSH) has been recently introduced as a well-tailored method for incorporating nuclear quantum effects, such as zero-point energy and tunneling, into nonadiabatic molecular dynamics simulations. The practical widespread usage of RPSH demands a comprehensive benchmarking of different reaction regimes and conditions with equal emphasis on demonstrating both the cons and the pros of the method. Here, we investigate the fundamental questions related to the conservation of energy and detailed balance in the context of RPSH. Using Tully's avoided crossing model as well as a 2-state quantum system coupled to a classical bath undergoing Langevin dynamics, we probe the critical problem of the proper treatment of the classically forbidden transitions stemming from the surface hopping algorithm. We show that proper treatment of these frustrated hops is key to the accurate description of real-time dynamics as well as reproducing the correct quantum Boltzmann populations.
