PyCTRAMER: A Python package for charge transfer rate constant of condensed-phase systems from Marcus theory to Fermi’s golden rule DOI
Zengkui Liu, Dominikus Brian, Xiang Sun

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(6)

Published: Aug. 9, 2024

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 semiclassical approximations Fermi’s golden rule (FGR) constant. It supports various types intramolecular intermolecular transitions excitonic states to state. Integrating quantum chemistry calculations, all-atom molecular dynamics (MD) simulations, spin-boson model construction, offers an automatic workflow handling photoinduced processes explicit solvent environments interfacial amorphous donor/acceptor blends. The also provides versatile tools individual steps, including electronic state analysis, state-specific force field MD construction energy trajectories. We demonstrate software’s capabilities through two examples, highlighting both prototypical OPV systems.

Language: Английский

Benchmarking various nonadiabatic semiclassical mapping dynamics methods with tensor-train thermo-field dynamics DOI
Zengkui Liu, Ningyi Lyu, Zhubin Hu

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(2)

Published: July 9, 2024

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 Ehrenfest mean-field fewest-switches surface hopping, linearized semiclassical dynamics, symmetrized quasiclassical spin-mapping method, extended classical models. Different model systems were evaluated, spin-boson condensed phase, linear vibronic coupling electronic transition through conical intersections, photoisomerization retinal, Tully’s one-dimensional scattering Our show that optimal choice dynamical method is system-specific, accuracy sensitively dependent zero-point-energy parameter initial sampling strategy variables.

Language: Английский

Citations

7
All-Atom Photoinduced Charge Transfer Dynamics in Condensed Phase via Multistate Nonlinear-Response Instantaneous Marcus Theory DOI Creative Commons
Zengkui Liu, Zailing Song, Xiang Sun

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(9), P. 3993 - 4006

Published: April 24, 2024

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 photoexcitation from equilibrium ground state provide time-dependent coefficient. In this work, we extend IMT method treating photoinduced among general multiple demonstrate organic photovoltaic carotenoid–porphyrin–fullerene triad dissolved explicit tetrahydrofuran solvent. All-atom molecular dynamics simulations were employed obtain time correlation functions gaps, which used generate IMT-required averages variances relevant gaps. Our calculations show that multistate could capture significant preparation, corroborated by substantial differences population predicted theory, where underestimates transfer. also shown have better agreement with nonadiabatic mapping than does. Because straightforward cost-effective implementation accounts effects, believe offers practical strategy studying complex condensed-phase systems.

Language: Английский

Citations

5
Non-equilibrium rate theory for polariton relaxation dynamics DOI
Yifan Lai, Wenxiang Ying, Pengfei Huo

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(10)

Published: Sept. 13, 2024

We derive an analytic expression of the non-equilibrium Fermi’s golden rule (NE-FGR) for a Holstein–Tavis–Cumming Hamiltonian, universal model many molecules collectively coupled to optical cavity. These NE-FGR expressions capture full-time-dependent behavior rate constant transitions from polariton states dark states. The is shown be reduced well-known frequency domain-based equilibrium (E-FGR) in and collective limit retain same scaling with number sites non-collective cases. use these perform population dynamics time-non-local time-local quantum master equation obtain accurate initially occupied upper or lower Furthermore, significantly improves accuracy when starting compared E-FGR theory, highlighting importance non-Markovian short-time transient transition constant.

Language: Английский

Citations

5
Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics DOI Creative Commons
Baihua Wu, Bingqi Li, Xin He

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Reliable trajectory-based nonadiabatic quantum dynamics methods at the atomic/molecular level are critical for practical understanding and rational design of many important processes in real large/complex systems, where dynamical behavior electrons that nuclei coupled. The paper reports latest progress field (NaF), a conceptually novel approach with independent trajectories. Substantially different from mainstreams Ehrenfest-like surface hopping methods, nuclear force NaF involves arising coupling between electronic states, addition to adiabatic contributed by single state. is capable faithfully describing interplay motion broad regime, which covers relevant states keep coupled wide range or all time bifurcation characteristic essential. derived exact generalized phase space formulation coordinate-momentum variables, constraint (CPS) employed discrete electronic-state degrees freedom (DOFs) infinite Wigner used continuous DOFs. We propose efficient integrators equations both diabatic representations. Since formalism CPS not unique, can principle be implemented various representations correlation function (TCF) time-dependent property. They applied suite representative gas-phase condensed-phase benchmark models numerically results available comparison. It shown relatively insensitive representation TCF will potential tool reliable simulations mechanical transition systems.

Language: Английский

Citations

0
Instantaneous Marcus theory for photoinduced charge transfer dynamics in multistate harmonic model systems DOI
Zengkui Liu, Xiang Sun

Journal of Physics Condensed Matter, Journal Year: 2024, Volume and Issue: 36(31), P. 315201 - 315201

Published: April 24, 2024

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 vertical photoexcitation equilibrated ground state, yielding time-dependent coefficient. The multistate harmonic (MSH) model Hamiltonian characterizes an organic photovoltaic carotenoid-porphyrin-fullerene triad dissolved explicit tetrahydrofuran solvent, constructed by mapping all-atom inputs molecular simulations. Our calculations reveal that population MSH models obtained with agree more accurate quantum-mechanical Fermi’s golden rule. This alignment suggests provides practical approach understanding nonadiabatic condensed-phase systems.

Language: Английский

Citations

3
Semiclassical approaches to perturbative time-convolution and time-convolutionless quantum master equations for electronic transitions in multistate systems DOI Creative Commons
Xiang Sun, Zengkui Liu

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(17)

Published: May 2, 2024

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 consistently incorporated, leading to a heterogeneous environment couples multiple states differently. Our exploration encompasses charge transfer organic photovoltaic carotenoid–porphyrin–C60 triad dissolved liquid solution excitation energy (EET) photosynthetic Fenna–Matthews–Olson complexes. By systematically comparing perturbative TC TCL QME approaches with exact quantum-mechanical various semiclassical approximate kernels, demonstrate their efficacy accuracy capturing essential features dynamics. calculations show QMEs generally yield more accurate results than QMEs, especially EET, although both methods offer versatile adaptable across different systems. addition, approximations featuring Wigner-transformed classical nuclear densities well governing during coherence period, highlighting trade-off between computational cost. This work provides valuable insights into applicability performance via model, offering guidance realistic applications condensed-phase atomistic level.

Language: Английский

Citations

3
Reduced density matrix dynamics in multistate harmonic models via time-convolution and time-convolutionless quantum master equations with quantum-mechanical and semiclassical kernels DOI
Xiang Sun, Zengkui Liu

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(18)

Published: Nov. 11, 2024

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 heterogeneous environments couple to multiple differently. We derive exact quantum-mechanical a hierarchy semiclassical approximate expressions for kernels in TC TCL QMEs project full RDM general shifted systems, including model. These applied simulate photoinduced charge transfer (PICT) organic photovoltaic carotenoid-porphyrin-fullerene triad solvated tetrahydrofuran solution excitation energy (EET) photosynthetic Fenna-Matthews-Olson complexes C. tepidum P. aestuarii. Our results show while both capture similar phenomena PICT EET processes, QME generally provides more accurate than QME, particularly initial oscillation population dynamics. This study highlights effectiveness modeling nonadiabatic offering insights realistic condensed phase systems.

Language: Английский

Citations

1
PyCTRAMER: A Python package for charge transfer rate constant of condensed-phase systems from Marcus theory to Fermi’s golden rule DOI
Zengkui Liu, Dominikus Brian, Xiang Sun

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 161(6)

Published: Aug. 9, 2024

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 semiclassical approximations Fermi’s golden rule (FGR) constant. It supports various types intramolecular intermolecular transitions excitonic states to state. Integrating quantum chemistry calculations, all-atom molecular dynamics (MD) simulations, spin-boson model construction, offers an automatic workflow handling photoinduced processes explicit solvent environments interfacial amorphous donor/acceptor blends. The also provides versatile tools individual steps, including electronic state analysis, state-specific force field MD construction energy trajectories. We demonstrate software’s capabilities through two examples, highlighting both prototypical OPV systems.

Language: Английский

Citations

0