Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space

Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space

May 15, 2024 | Xin He, Xiangsong Cheng, Baihua Wu, and Jian Liu
This article introduces a novel approach called NaF-TW (Nonadiabatic Field with Triangle Window Functions) for simulating nonadiabatic transition dynamics in quantum systems. The method uses triangle window functions (TWF) in conjunction with the constraint coordinate-momentum phase space (CPS) formulation to represent discrete electronic degrees of freedom (DOFs). The TWF approach is shown to be an exact representation of the population-population correlation function for two-state systems and is reasonably accurate for multistate systems. The NaF-TW approach is applied to model systems in both condensed and gas phases, demonstrating its ability to accurately capture the dynamical interplay between electronic and nuclear DOFs, including cases where states remain coupled and where nuclear motion exhibits bifurcation characteristics. The NaF-TW method is compared with other nonadiabatic dynamics approaches, such as surface hopping and Ehrenfest dynamics, and is shown to perform better in capturing the correct nuclear dynamics, especially in the asymptotic region where state coupling disappears. The method is particularly effective in handling the nonadiabatic coupling terms in the nuclear equations of motion, which are essential for accurately simulating nonadiabatic transitions. The NaF-TW approach is also shown to produce positive semidefinite population correlation functions, which is crucial for maintaining physical consistency in quantum simulations. The article presents benchmark tests on various model systems, including spin-boson models, the FMO monomer model, and cavity quantum electrodynamics (cQED) systems. These tests demonstrate that the NaF-TW approach outperforms other methods in accurately simulating electronic and nuclear dynamics, especially in complex systems where nonadiabatic coupling is significant. The results show that the NaF-TW approach is capable of capturing the correct asymptotic behavior and provides results that are close to exact data obtained from more accurate methods like MCTDH and DVR. The method is particularly effective in systems where the electronic states remain coupled, and it is shown to be more robust than conventional surface hopping approaches in such scenarios.This article introduces a novel approach called NaF-TW (Nonadiabatic Field with Triangle Window Functions) for simulating nonadiabatic transition dynamics in quantum systems. The method uses triangle window functions (TWF) in conjunction with the constraint coordinate-momentum phase space (CPS) formulation to represent discrete electronic degrees of freedom (DOFs). The TWF approach is shown to be an exact representation of the population-population correlation function for two-state systems and is reasonably accurate for multistate systems. The NaF-TW approach is applied to model systems in both condensed and gas phases, demonstrating its ability to accurately capture the dynamical interplay between electronic and nuclear DOFs, including cases where states remain coupled and where nuclear motion exhibits bifurcation characteristics. The NaF-TW method is compared with other nonadiabatic dynamics approaches, such as surface hopping and Ehrenfest dynamics, and is shown to perform better in capturing the correct nuclear dynamics, especially in the asymptotic region where state coupling disappears. The method is particularly effective in handling the nonadiabatic coupling terms in the nuclear equations of motion, which are essential for accurately simulating nonadiabatic transitions. The NaF-TW approach is also shown to produce positive semidefinite population correlation functions, which is crucial for maintaining physical consistency in quantum simulations. The article presents benchmark tests on various model systems, including spin-boson models, the FMO monomer model, and cavity quantum electrodynamics (cQED) systems. These tests demonstrate that the NaF-TW approach outperforms other methods in accurately simulating electronic and nuclear dynamics, especially in complex systems where nonadiabatic coupling is significant. The results show that the NaF-TW approach is capable of capturing the correct asymptotic behavior and provides results that are close to exact data obtained from more accurate methods like MCTDH and DVR. The method is particularly effective in systems where the electronic states remain coupled, and it is shown to be more robust than conventional surface hopping approaches in such scenarios.
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