论文标题
量子古典的liouville形式主义在预先的基础上及其与相空间跳跃的联系
A Quantum-Classical Liouville Formalism in a Preconditioned Basis and Its Connection with Phase-Space Surface Hopping
论文作者
论文摘要
我们通过使用伪耐绝化基础的相位空间表面跳跃（PSSH）算法来重新审视一项最新的建议，该提案通过相位空间跳跃（PSSH）算法对非绝热问题进行建模。在这里，我们表明，这种伪造的PSSH（PD-PSSH）ANSATZ与可以在预处理过程后可以得出的量子古典liouville方程（QCLE）一致，我们证明了适当的PD-PSSH算法能够捕获某些几何磁性效果（以及标准的fssh方法）。我们还发现，在某些情况下，预处理的QCLE可以胜过标准QCL，这强调了没有唯一的QCLE的事实。最后，我们还指出，可以使用类似于PSSH所做的相位空间表示形式来构造平均田间eHrenfest算法。在理解和模拟复杂的哈密顿量和/或自旋退化的情况下，这些发现似乎非常有用。
We revisit a recent proposal to model nonadiabatic problems with a complex-valued Hamiltonian through a phase-space surface hopping (PSSH) algorithm employing a pseudo-diabatic basis. Here, we show that such a pseudo-diabatic PSSH (PD-PSSH) ansatz is consistent with a quantum-classical Liouville equation (QCLE) that can be derived following a preconditioning process, and we demonstrate that a proper PD-PSSH algorithm is able to capture some geometric magnetic effects (whereas the standard FSSH approach cannot). We also find that a preconditioned QCLE can outperform the standard QCLE in certain cases, highlighting the fact that there is no unique QCLE. Lastly, we also point out that one can construct a mean-field Ehrenfest algorithm using a phase-space representation similar to what is done for PSSH. These findings would appear extremely helpful as far understanding and simulating nonadiabatic dynamics with complex-valued Hamiltonians and/or spin degeneracy.
