Twin-Space Representation of Classical Mapping Model in the Constraint Phase Space Representation: Numerically Exact...

The constraint coordinate-momentum phase space (CPS) has recently been developed to study nonadiabatic dynamics in gas-phase and condensed-phase molecular systems. Although the CPS formulation is exact for describing the discrete (electronic/vibrational/spin) state degrees of freedom (DOFs), when system-bath models in condensed phase are studied, previous works often employ the approximation by discretizing environmental bath DOFs. In this paper, we develop an exact trajectory-based phase space approach by adopting the twin-space (TS) formulation of quantum statistical mechanics, in which the density operator of the reduced system is transformed to the wave function of an expanded system with twice the DOFs. The classical mapping model (CMM) is then used to map the Hamiltonian of the expanded system to its equivalent classical counterpart on CPS. To demonstrate the applicability of the TS-CMM approach, we compare simulated population dynamics and nonlinear spectra for a few benchmark condensed phase system-bath models with those obtained from the hierarchical equations of motion method, which shows that our approach yields accurate dynamics of open quantum systems.