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 recently proposed multi-state harmonic (MSH) model Hamiltonian. MSH models were constructed faithfully capture photoinduced charge transfer dynamics a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad dissolved tetrahydrofuran. A general expression of fully quantum-mechanical...

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

Accurate quantum dynamics simulations of nonadiabatic processes are important for studies electron transfer, energy and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation high-dimensional arrays, including TT-KSL zero-temperature TT-thermofield finite-temperature dynamics. The investigated include mixed quantum–classical...

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

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

An elegant integration of light-emitting segments into the structure polymeric delivery systems endows resulting self-assembled nanovehicles with diagnostic ability toward an enhanced therapeutic efficiency. A variety polyfluorene (PF)-based binary were designed and developed successfully, but PF-based ternary formulations remain rarely explored, likely due to synthetic challenge. To develop a universal synthesis strategy linear conjugated amphiphilic triblock copolymer for cancer...

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...

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 terms of effective spin-boson model Hamiltonian. Extending this photoinduced processes requires also taking into consideration ground state addition excited states. In paper, we revisit problem describing such nonequilibrium three-state harmonic model. We do so within framework Fermi’s...

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. most widely used Frenkel exciton model FMO assumes that each excited bacteriochlorophyll site couples to an identical and isolated harmonic bath, which does not account the heterogeneous local environment. To better describe realistic environment, we propose use recently developed multistate (MSH)...

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 evaluating the two-state symmetrized TCFs. Expressing forward and backward propagation different electronic potential energy surfaces complex-time path integral, then transform variables to average difference that integration over...

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 restructured and enriched version of the CTRAMER (Charge-Transfer RAtes from Molecular dynamics, Electronic structure, Rate theory) [Tinnin et al. J. Chem. Phys. 154, 214108 (2021)], enabling computation Marcus CT constant six levels linearized...

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 couplings within framework of multistate harmonic (MSH) models. The MSH model Hamiltonian consistently incorporates electronic-vibrational correlations between all pairs states by satisfying pairwise reorganization energies directly obtained from all-atom simulations, representing globally...

We report the observation and assignment of rotational spectra dibenzofuran measured in range 2–6 GHz with a newly constructed broadband chirped-pulse Fourier transform microwave (cp-FTMW) spectrometer. An analysis led to 40 b-type transitions, resulting accurate determination constants A=2278.19770(38) MHz, B=601.12248(10) C=475.753120(98) MHz.

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 recently proposed multi-state harmonic (MSH) model Hamiltonian. The MSH models were constructed for faithfully capturing photoinduced charge transfer dynamics a prototypical organic photovoltaic carotenoid-porphyrin-C60 molecular triad dissolved tetrahydrofuran. A general expression of fully quantum-mechanical...