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Reduced density matrix dynamics in multistate harmonic models via time-convolution and time-convolutionless quantum
1Division of Arts and Sciences, NYU Shanghai, 567 West Yangsi Road, Shanghai 200124, China; NYU-ECNU Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China; and Department of Chemistry, New York University, New York, New York 10003, USA.
The Journal of Chemical Physics
|November 11, 2024
Summary
This study compares time-convolution (TC) and time-convolutionless (TCL) quantum master equations (QMEs) for modeling electronic reduced density matrix (RDM) dynamics. TC QME generally offers more accurate results for nonadiabatic processes like photoinduced charge transfer and excitation energy transfer.
Area of Science:
- Theoretical Chemistry
- Quantum Dynamics
- Spectroscopy
Background:
- Modeling electronic dynamics in complex systems requires accurate quantum master equations (QMEs).
- Multistate harmonic (MSH) models capture electronic-vibrational correlations in heterogeneous environments.
- Photoinduced charge transfer (PICT) and excitation energy transfer (EET) are crucial processes in molecular systems.
Purpose of the Study:
- To explore and compare the performance of time-convolution (TC) and time-convolutionless (TCL) QMEs for simulating electronic reduced density matrix (RDM) dynamics.
- To investigate the applicability of TC and TCL QMEs within the multistate harmonic (MSH) model framework for realistic condensed phase systems.
- To provide insights into the dynamics of photoinduced charge transfer (PICT) and excitation energy transfer (EET) processes.
Main Methods:
- Derivation of exact quantum-mechanical and semiclassical approximate expressions for kernels in TC and TCL QMEs.
- Application of TC and TCL QMEs based on perturbative electronic couplings and MSH models.
- Simulation of RDM dynamics for PICT in a carotenoid-porphyrin-fullerene triad and EET in Fenna-Matthews-Olson complexes.
Main Results:
- Both TC and TCL QMEs successfully capture key phenomena in PICT and EET dynamics.
- TC QME demonstrates superior accuracy compared to TCL QME, especially in the initial dynamics of EET population.
- The MSH model effectively incorporates electronic-vibrational correlations and environmental heterogeneity.
Conclusions:
- TC and TCL QMEs are effective tools for modeling RDM dynamics in nonadiabatic processes.
- TC QME provides a more accurate description of quantum dynamics, particularly for systems exhibiting oscillatory behavior.
- This work offers valuable insights for simulating complex condensed phase systems relevant to photovoltaics and photosynthesis.
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