Reduced density matrix dynamics in multistate harmonic models via time-convolution and time-convolutionless quantum master equations with quantum-mechanical and semiclassical kernels.

In this work, we explore the electronic reduced density matrix (RDM) dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) that are based on perturbative electronic couplings within the framework of multistate harmonic (MSH) models. The MSH model Hamiltonian consistently incorporates the electronic-vibrational correlations between all pairs of states by satisfying the pairwise reorganization energies directly obtained from all-atom simulations, representing the globally heterogeneous environments that couple to the multiple states differently. We derive the exact quantum-mechanical and a hierarchy of semiclassical approximate expressions for the kernels in TC and TCL QMEs that project the full RDM for general shifted harmonic systems, including the MSH model.

PyCTRAMER: A Python package for charge transfer rate constant of condensed-phase systems from Marcus theory to Fermi's golden rule.

In this work, we introduce PyCTRAMER, a comprehensive Python package designed for calculating charge transfer (CT) rate constants in disordered condensed-phase systems at finite temperatures, such as organic photovoltaic (OPV) materials. PyCTRAMER is a restructured and enriched version of the CTRAMER (Charge-Transfer RAtes from Molecular dynamics, Electronic structure, and Rate theory) package [Tinnin et al. J.

Benchmarking various nonadiabatic semiclassical mapping dynamics methods with tensor-train thermo-field dynamics.

Accurate quantum dynamics simulations of nonadiabatic processes are important for studies of electron transfer, energy transfer, and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate nonadiabatic dynamics methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation of high-dimensional arrays, including TT-KSL for zero-temperature dynamics and TT-thermofield dynamics for finite-temperature dynamics. The approximate nonadiabatic dynamics methods investigated include mixed quantum-classical Ehrenfest mean-field and fewest-switches surface hopping, linearized semiclassical mapping dynamics, symmetrized quasiclassical dynamics, the spin-mapping method, and extended classical mapping models.

Semiclassical approaches to perturbative time-convolution and time-convolutionless quantum master equations for electronic transitions in multistate systems.

Understanding the dynamics of photoinduced processes in complex systems is crucial for the development of advanced energy-conversion materials. In this study, we investigate the nonadiabatic dynamics using time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) based on treating electronic couplings as perturbation within the framework of multistate harmonic (MSH) models. The MSH model Hamiltonians are mapped from all-atom simulations such that all pairwise reorganization energies are consistently incorporated, leading to a heterogeneous environment that couples to the multiple electronic states differently.

Instantaneous Marcus theory for photoinduced charge transfer dynamics in multistate harmonic model systems.

Modeling the dynamics of photoinduced charge transfer (CT) in condensed phases presents challenges due to complicated many-body interactions and the quantum nature of electronic transitions. While traditional Marcus theory is a robust method for calculating CT rate constants between electronic states, it cannot account for the nonequilibrium effects arising from the initial nuclear state preparation. In this study, we employ the instantaneous Marcus theory (IMT) to simulate photoinduced CT dynamics.

All-Atom Photoinduced Charge Transfer Dynamics in Condensed Phase via Multistate Nonlinear-Response Instantaneous Marcus Theory.

Photoinduced charge transfer (CT) in the condensed phase is an essential component in solar energy conversion, but it is challenging to simulate such a process on the all-atom level. The traditional Marcus theory has been utilized for obtaining CT rate constants between pairs of electronic states but cannot account for the nonequilibrium effects due to the initial nuclear preparation. The recently proposed instantaneous Marcus theory (IMT) and its nonlinear-response formulation allow for incorporating the nonequilibrium nuclear relaxation to electronic transition between two states after the photoexcitation from the equilibrium ground state and provide the time-dependent rate coefficient.

Generalized nonequilibrium Fermi's golden rule and its semiclassical approximations for electronic transitions between multiple states.

The nonequilibrium Fermi's golden rule (NE-FGR) approach is developed to simulate the electronic transitions between multiple excited states in complex condensed-phase systems described by the recently proposed multi-state harmonic (MSH) model Hamiltonian. The MSH models were constructed to faithfully capture the photoinduced charge transfer dynamics in a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad dissolved in tetrahydrofuran. A general expression of the fully quantum-mechanical NE-FGR rate coefficients for transitions between all pairs of states in the MSH model is obtained.

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

Constructing multistate model Hamiltonians from all-atom electronic structure calculations and molecular dynamics simulations is crucial for understanding charge and energy transfer dynamics in complex condensed phases. The most popular two-level system model is the spin-boson Hamiltonian, where the nuclear degrees of freedom are represented as shifted normal modes. Recently, we proposed the general multistate nontrivial extension of the spin-boson model, i.

Effects of Heterogeneous Protein Environment on Excitation Energy Transfer Dynamics in the Fenna-Matthews-Olson Complex.

The Fenna-Matthews-Olson (FMO) complex of green sulfur bacteria has been serving as a prototypical light-harvesting protein for studying excitation energy transfer (EET) dynamics in photosynthesis. The most widely used Frenkel exciton model for FMO complex assumes that each excited bacteriochlorophyll site couples to an identical and isolated harmonic bath, which does not account for the heterogeneous local protein environment. To better describe the realistic environment, we propose to use the recently developed multistate harmonic (MSH) model, which contains a globally shared bath that couples to the different pigment sites according to the atomistic quantum mechanics/molecular mechanics simulations with explicit protein scaffold and solvent.

Imaginary-time open-chain path-integral approach for two-state time correlation functions and applications in charge transfer.

Quantum time correlation functions (TCFs) involving two states are important for describing nonadiabatic dynamical processes such as charge transfer (CT). Based on a previous single-state method, we propose an imaginary-time open-chain path-integral (OCPI) approach for evaluating the two-state symmetrized TCFs. Expressing the forward and backward propagation on different electronic potential energy surfaces as a complex-time path integral, we then transform the path variables to average and difference variables such that the integration over the difference variables up to the second order can be performed analytically.

Three-state harmonic models for photoinduced charge transfer.

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.

Fabrication of Conjugated Amphiphilic Triblock Copolymer for Drug Delivery and Fluorescence Cell Imaging.

An elegant integration of light-emitting segments into the structure of polymeric delivery systems endows the resulting self-assembled nanovehicles with the diagnostic ability toward an enhanced therapeutic efficiency. A variety of polyfluorene (PF)-based binary delivery systems were designed and developed successfully, but PF-based ternary formulations remain rarely explored, likely due to the synthetic challenge. To develop a universal synthesis strategy toward linear conjugated amphiphilic triblock copolymer for cancer theranostics, herein we focused on the functionalization of the PF terminus for further chain extension and prepared well-defined PF-based amphiphilic triblock copolymers, PF--poly(ε-caprolactone)--poly(oligo(ethylene glycol) monomethyl ether methacrylate) (PF--PCL--POEGMA), by integrated state-of-the-art polymer chemistry techniques, including Suzuki reaction, ring-opening polymerization, atom transfer radical polymerization, and click coupling.