Department of Physics, Rutgers University, Newark, New Jersey 07102, USA.
J Chem Phys. 2023 Apr 28;158(16). doi: 10.1063/5.0149116.
The coupled-trajectory mixed quantum-classical method (CTMQC), derived from the exact factorization approach, has successfully predicted photo-chemical dynamics in a number of interesting molecules, capturing population transfer and decoherence from first principles. However, due to the approximations made, CTMQC does not guarantee energy conservation. We propose a modified algorithm, CTMQC-E, which redefines the integrated force in the coupled-trajectory term so to restore energy conservation, and demonstrate its accuracy on scattering in Tully's extended coupling region model and photoisomerization in a retinal chromophore model.
耦合轨迹混合量子经典方法（CTMQC）源于精确因式分解方法，已成功预测了许多有趣分子的光化学反应动力学，从第一性原理捕获了种群转移和去相干。然而，由于所做的近似，CTMQC 不能保证能量守恒。我们提出了一种改进的算法 CTMQC-E，它重新定义了耦合轨迹项中的积分力，以恢复能量守恒，并在 Tully 的扩展耦合区域模型中的散射和视黄醛模型中的光异构化中验证了其准确性。
