Model Hamiltonians constructed from quantum chemistry calculations and molecular dynamics simulations are widely used for simulating nonadiabatic dynamics in the condensed phase. The most popular two-state spin-boson model could be built by mapping the all-atom anharmonic Hamiltonian onto a two-level system bilinearly coupled to a harmonic bath using the energy gap time correlation function. However, for more than two states, there lacks a general strategy to construct multi-state harmonic (MSH) models since the energy gaps between different pairs of electronic states are not entirely independent and need to be considered consistently. In this paper, we extend the previously proposed approach for building three-state harmonic models for photoinduced charge transfer to the arbitrary number of electronic states with a globally shared bath and the system–bath couplings are scaled differently according to the reorganization energies between each pair of states. We demonstrate the MSH model construction for an organic photovoltaic carotenoid–porphyrin–C60 molecular triad dissolved in explicit tetrahydrofuran solvent. Nonadiabatic dynamics was simulated using mixed quantum-classical techniques, including the linearized semiclassical and symmetrical quasiclassical dynamics with the mapping Hamiltonians, mean-field Ehrenfest, and mixed quantum-classical Liouville dynamics in two-state, three-state, and four-state harmonic models of the triad system. The MSH models are shown to provide a general and flexible framework for simulating nonadiabatic dynamics in complex systems.

Instantaneous Marcus theory (IMT) offers a way for capturing the time-dependent charge transfer (CT) rate coefficient in nonequilibrium photoinduced CT processes, where the system was photoexcited from its equilibrated ground state vertically to the excitonic state, followed by an electronic transition to the CT state. As derived from the linearized semiclassical nonequilibrium Fermi's golden rule (LSC NE-FGR), the original IMT requires expensive all-atom nonequilibrium molecular dynamics (NEMD) simulations. In this work, we propose computationally efficient linear-response and nonlinear-response formulations for IMT rate calculations, which only require equilibrium molecular dynamics simulations. The linear-and nonlinear-response IMT methods were tested to predict the transient behavior in the photoinduced CT dynamics of the carotenoid−porphyrin−C 60 molecular triad solvated in explicit tetrahydrofuran. Our result demonstrated that the nonlinear-response IMT is in excellent agreement with the benchmark NEMD for all cases investigated here, whereas the linear-response IMT predicts the correct trend for all cases but overestimates the transient CT rate in one case involving a significant nonequilibrium relaxation. This mild breakdown of linear-response IMT is due to neglecting the higher-order terms in the exact nonlinear-response IMT. Taking advantage of time translational symmetry, the linear-and nonlinearresponse approaches were demonstrated to be able to reduce the computational cost by 80% and 60% compared with NEMD simulations, respectively. Thus, we highly recommend the readily applicable and accurate nonlinear-response IMT approach for simulating nonequilibrium CT processes in complex molecular systems in the condensed phase.

A widely used strategy for simulating the charge transfer between donor and acceptor electronic states in an all-atom anharmonic condensed-phase system is based on invoking linear response theory to describe the system in terms of an effective spin-boson model Hamiltonian. Extending this strategy to photoinduced charge transfer processes requires also taking into consideration the ground electronic state in addition to the excited donor and acceptor electronic states. In this paper, we revisit the problem of describing such nonequilibrium processes in terms of an effective three-state harmonic model. We do so within the framework of nonequilibrium Fermi’s golden rule (NE-FGR) in the context of photoinduced charge transfer in the carotenoid–porphyrin–C60 (CPC60) molecular triad dissolved in explicit tetrahydrofuran (THF). To this end, we consider different ways for obtaining a three-state harmonic model from the equilibrium autocorrelation functions of the donor–acceptor, donor–ground, and acceptor–ground energy gaps, as obtained from all-atom molecular dynamics simulations of the CPC60/THF system. The quantum-mechanically exact time-dependent NE-FGR rate coefficients for two different charge transfer processes in two different triad conformations are then calculated using the effective three-state model Hamiltonians as well as a hierarchy of more approximate expressions that lead to the instantaneous Marcus theory limit. Our results show that the photoinduced charge transfer in CPC60/THF can be described accurately by the effective harmonic three-state models and that nuclear quantum effects are small in this system.