Multistate Reaction Coordinate Model for Charge and Energy Transfer Dynamics in the Condensed Phase

• DOI: 10.1021/acs.jctc.3c00770
• Publication Date: 2023-10-10T16:56:28Z
• Authors: Zengkui Liu; Haorui Hu; Xiang Sun
• Keywords: Hamiltonian (control theory); Reaction coordinate

Constructing multistate model Hamiltonians from all-atom electronic structure calculations and molecular dynamics simulations is crucial for understanding charge energy transfer in complex condensed phases. The most popular two-level system the spin-boson Hamiltonian, where nuclear degrees of freedom are represented as shifted normal modes. Recently, we proposed general nontrivial extension model, i.e., harmonic (MSH) which constructed by extending spatial dimensions each mode so to satisfy reorganization restrictions all pairs states. In this work, propose reaction coordinate (MRC) with a primary secondary bath modes Caldeira-Leggett form but extended dimensions. MRC proven be equivalent MSH offers an intuitive physical picture nuclear-electronic feedback nonadiabatic processes such inherent trajectory coordinate. dimensions, carrying entire energies bilinearly coupled We demonstrate construction photoinduced organic photovoltaic caroteniod-porphyrin-C60 triad dissolved tetrahydrofuran well excitation photosynthetic light-harvesting Fenna-Matthews-Olson complex. provides effective robust platform investigating quantum dissipative condensed-phase systems since it allows consistent description realistic spectral density, state-dependent system-bath couplings, heterogeneous environments due static disorder energies.