A hybrid memory kernel approach for condensed phase non-adiabatic dynamics.

Abstract

The spin-boson model is a simplified Hamiltonian often used to study non-adiabatic dynamics in large condensed phase systems, even though it has not been solved in a fully analytic fashion. Herein, we present an exact analytic expression for the dynamics of the spin-boson model in the infinitely slow-bath limit and generalize it to approximate dynamics for faster baths. We achieve the latter by developing a hybrid approach that combines the exact slow-bath result with the popular non-interacting blip approximation (NIBA) method to generate a memory kernel that is formally exact to second-order in the diabatic coupling but also contains higher-order contributions approximated from the second-order term alone. This kernel has the same computational complexity as the NIBA, but is found to yield dramatically superior dynamics in regimes where the NIBA breaks down-such as systems with large diabatic coupling or energy bias. This indicates that this hybrid approach could be used to cheaply incorporate higher-order effects into second-order methods and could potentially be generalized to develop alternate kernel resummation schemes.