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Journal of Chemical Theory and Computation

TD-DMRG Study of Exciton Dynamics with both Thermal and Static Disorders for Fenna-Matthews-Olson Complex

Zirui Sheng, Tong Jiang, Weitang Li, Zhigang Shuai

Published Aug 1, 2024• 10 citations

Abstract

Photosynthesis is a fundamental process that converts solar energy into chemical energy. Understanding the microscopic mechanisms of energy transfer in photosynthetic systems is crucial for the development of novel optoelectronic materials. Simulating these processes poses significant challenges due to the intricate interactions between electrons and phonons, compounded by static disorder. In this work, we present a numerically nearly exact study using the time-dependent density matrix renormalization group (TD-DMRG) method to simulate the quantum dynamics of the Fenna-Matthews-Olson (FMO) complex considering an eight-site model with both thermal and static disorders. We employ the thermo-field dynamics formalism for temperature effects. We merge all electronic interactions into one large matrix product state (MPS) site, boosting accuracy efficiently without increasing complexity. Previous combined experimental and computational studies indicated that the static disorders range from 30 to 90 cm –1 for different FMO sites. We employ a Gaussian distribution and the auxiliary bosonic operator approach to consider the static disorder in our TD-DMRG algorithm. We investigate the impact of different initial excitation sites, temperatures, and degrees of static disorder on the exciton dynamics and temporal coherence. It is found that under the influence of the experimentally determined static disorder strength, the exciton population evolution shows a non-negligible difference at zero temperature, while it is hardly affected at room temperature.

DOI: 10.1021/acs.jctc.4c00493

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Photosynthesis is a fundamental process that converts solar energy into chemical energy. Understanding the microscopic mechanisms of energy transfer in photosynthetic systems is crucial for the development of novel optoelectronic materials. Simulating these processes poses significant challenges due to the intricate interactions between electrons and phonons, compounded by static disorder. In this work, we present a numerically nearly exact study using the time-dependent density matrix renormalization group (TD-DMRG) method to simulate the quantum dynamics of the Fenna-Matthews-Olson (FMO) complex considering an eight-site model with both thermal and static disorders. We employ the thermo-field dynamics formalism for temperature effects. We merge all electronic interactions into one large matrix product state (MPS) site, boosting accuracy efficiently without increasing complexity. Previous combined experimental and computational studies indicated that the static disorders range from 30 to 90 cm –1 for different FMO sites. We employ a Gaussian distribution and the auxiliary bosonic operator approach to consider the static disorder in our TD-DMRG algorithm. We investigate the impact of different initial excitation sites, temperatures, and degrees of static disorder on the exciton dynamics and temporal coherence. It is found that under the influence of the experimentally determined static disorder strength, the exciton population evolution shows a non-negligible difference at zero temperature, while it is hardly affected at room temperature.

Recent advances in experimental techniques have enabled precise characterization of fundamental nonadiabatic and even electronic dynamics in molecules, on ultrafast time scales reaching femtosecond to attosecond resolution. However, accurate theoretical simulation of these ultrafast chemical dynamics processes in large systems remains challenging, largely due to the overwhelming number of degrees of freedom (DoFs) and the pronounced many-body correlations. In recent years, by leveraging efficient decomposition schemes for high-dimensional wave function and operator tensors, the time-dependent density matrix renormalization group (TD-DMRG) has emerged as a powerful and accurate quantum dynamics method for simulating nonadiabatic and electron dynamics in large chemical systems, in conjunction with realistic electron/exciton-vibration/phonon models or ab initio quantum chemistry many-electron Hamiltonians. This review outlines the fundamentals of TD-DMRG for chemical dynamics, covering matrix product state/operator (MPS/MPO) frameworks and algorithms from ground-state calculations to time evolution. We discuss thermal/environmental effects and compare TD-DMRG with other tensor network methods such as multiconfiguration time-dependent Hartree (MCTDH) and multilayer MCTDH (ML-MCTDH). Demonstrated applications include simulations of pyrazine absorption, singlet fission in rubrene crystal, and charge migration in chloroacetylene cation. These show TD-DMRG’s capability for modeling complex ultrafast processes from femtoseconds to attoseconds with controlled accuracy.

In this Article we perform a systematic study of the global entanglement and exciton coherence length dynamics coherence in natural light-harvesting system Fenna-Matthews-Olson (FMO) complex across various parameters of a dissipative environment from low to high temperatures, weak to strong system-environment coupling, and non-Markovian environments. A non-perturbative numerically exact hierarchical equations of motions method is employed to propagate the dynamics of the system. We found that entanglement is driven primarily by the strength of interaction between the system and environment, and it is modulated by the interplay between temperature and non-Markovianity. In contrast, coherence length is found to be insensitive to non-Markovianity. Furthermore, our results do not show the direct correlation between global entanglement and the efficiency of the excitation energy transfer in the FMO complex

In this article, we perform a systematic study of the global entanglement and exciton coherence length dynamics in natural light-harvesting system Fenna-Matthews-Olson (FMO) complex across various parameters of a dissipative environment from low to high temperatures, weak to strong system-environment coupling, and non-Markovian environments. A nonperturbative numerically exact hierarchical equations of motions method is employed to obtain the dynamics of the system. We found that entanglement is driven primarily by the strength of interaction between the system and environment, and it is modulated by the interplay between temperature and non-Markovianity. In contrast, coherence length is found to be insensitive to non-Markovianity. In agreement with previous studies, we do not observe a direct correlation between global entanglement and the efficiency of the excitation energy transfer in the FMO complex. As a new result, we found that the coherence length dynamics is correlated with the excitation energy transfer dynamics.

We study the evolution of quantum entanglement during exciton energy transfer (EET) in a network model of the Fenna-Matthews-Olson (FMO) complex, a biological pigment-protein complex involved in the early steps of photosynthesis in sulfur bacteria. The influence of Markovian as well as spatially and temporally correlated (non-Markovian) noise on the generation of entanglement across distinct chromophores (site entanglement) and different excitonic eigenstates (mode entanglement) is studied for different injection mechanisms, including thermal and coherent laser excitation. Additionally, we study the entangling power of the FMO complex under natural operating conditions. While quantum information processing tends to favor maximal entanglement, near unit EET is achieved as the result of an intricate interplay between coherent and noisy processes where the initial part of the evolution displays intermediate values of both forms of entanglement.

The dynamics of energy transfer in Fenna–Matthews–Olson (FMO) light-harvesting complex interacting with a phonon bath is investigated. In this contribution, by considering the phonon bath as a source of stochastic noise, a new approach is proposed. Also, by calculating the global quantum entanglement and global quantum discord, the time evolution of the quantum correlation during the process is evaluated. The effects of temperature and initial excited state on the energy transfer and the quantum correlation are studied. It is shown, in agreement with the previous results, that the increasing of the temperature gives rise to the faster delocalisation of energy transfer and global quantum entanglement in the FMO complex. The proposed model predicts that the global discord is resistance versus the raising temperature. Furthermore, it is demonstrated that the quantum entanglement with respect to the global quantum discord has a significant role in the process of energy transfer in the FMO complex.

Time dependent density matrix renormalization group (TD-DMRG) has become one of the cutting edge methods of quantum dynamics for complex systems. In this paper, we comparatively study the accuracy and efficiency for three time evolution schemes in TD-DMRG method, the direct propagation and compression with 4th order Runge-Kutta propagator (P&C-RK4), time dependent variational principle with matrix unfolding (TDVP-MU) and projector splitting (PS) by performing benchmarks on the exciton dynamics of Fenna-Matthews-Olson (FMO) complex. We show that the PS scheme is the most accurate and the fastest method because the propagation in each step is unitary by combining Krylov subspace algorithm and there is no error caused by regularization or instability of matrix inversion. We also compare the parallelization efficiency of multi-core central processing units (CPU) with graphical processing units (GPU) and we find that although 28 cores of CPU can merely double the speed, GPU is able to speed up the TDVP-MU and PS scheme by up to 57 times through efficient acceleration of matrix multiplication. Using the optimal strategy, we are able to simulate the full quantum exciton dynamics of 7-site FMO model with 252 degrees of freedom to a timescale of 1 ps at fairly high accuracy within only 4 minutes.