Extending ring polymer molecular dynamics rate theory to reactions with non-separable reactants

Abstract

The ring polymer molecular dynamics (RPMD) rate theory is an efficient and accurate method for estimating rate coefficients of chemical reactions affected by nuclear quantum effects. The commonly used RPMD treatment of gas-phase bimolecular reactions adopts two dividing surfaces, one at the transition state and another in the reactant asymptote, where partition functions of separated reactants can be readily obtained. With some exceptions, however, this strategy is difficult to implement for processes on surfaces or in liquids, because the reactants are often strongly coupled with the extended medium (surface or solvent) and thus non-separable. Under such circumstances, the RPMD rate theory with a single dividing surface (SDS) is better suited. However, most of its implementations adopted Cartesian forms of the reaction coordinate, which, in many cases, are not ideal for describing complex reactions. Here, we present a SDS-based RPMD implementation, which are able to tackle the aforementioned challenges. This approach is demonstrated in four representative reactions, including the gas phase H + H2 exchange reaction, gas phase CH3NC isomerization, H recombinative desorption from Pt(111), and NO desorption from Pd(111). This implementation, which is applicable to both uni- and bi-molecular reactions, offers a unified treatment of gas-phase and surface reaction rate calculations on the same footing.