Quantum-mechanical reaction rate constants from centroid molecular dynamics simulations: Barrier crossing in an asymmetrical double-well

Quantum-mechanical reaction rate constants were calculated from centroid molecular dynamics (CMD) simulations, for the case of barrier crossing in an asymmetrical double-well potential bilinearly coupled to a harmonic bath. The calculation is based on a recently proposed formulation of the reaction rate constant in terms of the position—flux correlation function, which can be approximated via CMD in a well-defined manner. The predictions of CMD and various simplified versions of it are compared to exact results, which were obtained via the quasi-adiabatic propagator path integral (QUAPI) method, and/or path integral quantum transition state theory (PI-QTST). The predictions based on CMD are found to be in good agreement with both.