论文标题
随机多配置时间依赖于耗散量子动力学的时间依赖性hartree具有强分子内耦合
Stochastic Multi Configuration Time-Dependent Hartree for Dissipative Quantum Dynamics with Strong Intramolecular Coupling
论文作者
论文摘要
在本文中，我们探讨了在系统浴方法之后，与马尔可夫浴室接触的强耦合多维系统的耗散动力学。我们在这项努力中使用了最近开发的随机多种配置时间依赖于时间依赖的Hartree方法在蒙特卡洛波数据包形式主义[J.chem.phys.156，094109（2022）]中。事实证明，当分子内耦合较弱时，该方法可产生波包的热合团。为了治疗强耦合系统，新的Lindblad耗散算子被构造为系统坐标和相关矩的线性组合。这些是通过统一转换为正常模式表示的，该表示将耦合到二阶的互联面降低。此外，我们使用广义升高/降低操作员的组合来强制耗散算子中的玻尔兹曼分布，从而在谐波极限中产生完美的热化。使用二维哈密顿量参数的模型测试了两个ANSATZ，以解开分子内电位耦合的影响，该耦合的效果，在费米共振中观察到的强模式混合和非谐度。
In this article, we explore the dissipation dynamics of a strongly coupled multidimensional system in contact with a Markovian bath following a system-bath approach. We use in this endeavour the recently developed stochastic Multi-Configuration Time-Dependent Hartree approach within the Monte Carlo wave packet formalism [J.Chem.Phys.156, 094109 (2022)]. The method proved to yield thermalized ensembles of wave packets when intramolecular coupling is weak. To treat strongly coupled systems, new Lindblad dissipative operators are constructed as linear combinations of the system coordinates and associated momenta. These are obtained by an unitary transformation to a normal mode representation, which reduces intermode coupling up to second order. Additionally, we use combinations of generalized raising/lowering operators to enforce the Boltzmann distribution in the dissipation operators, which yield perfect thermalization in the harmonic limit. The two ansatz are tested using a model two-dimensional hamiltonian parameterized to disentangle the effects of intramolecular potential coupling, of strong mode mixing observed in Fermi resonances, and of anharmonicity.
