论文标题

超快量子分子动力学的实验室框架密度矩阵

A Laboratory Frame Density Matrix for Ultrafast Quantum Molecular Dynamics

论文作者

Gregory, Margaret, Neville, Simon, Schuurman, Michael, Makhija, Varun

论文摘要

在大多数情况下,考虑了共鸣分子的超快动力学,并且几乎总是在分子框架中计算,而实验则在实验室框架中进行。在这里,我们用实验室框架密度矩阵提供形式主义,该矩阵将分子框架中的量子动力学连接到实验室框架中的量子动力学,从而在计算与测量之间提供了透明的联系。形式主义表明,在任何此类实验中,分子框架动力学的动力学因不同方向的分子而有所不同,并且某些可能在实验上可以访问的连贯性会被降低的振动密度矩阵拒绝。取而代之的是,将分子角分布矩(MADMS)引入,作为更准确的实验访问信息的代表。此外,形式主义提供了对分子框架量子断层扫描的明确定义,并指定了执行这种测量的要求,从而实现了分子框架振动动力学的实验成像。成功完成此类测量值完全表征了在实验室框架中任何方向上分子的分子框架量子动力学。

In most cases the ultrafast dynamics of resonantly excited molecules are considered, and almost always computed in the molecular frame, while experiments are carried out in the laboratory frame. Here we provide a formalism in terms of a lab frame density matrix which connects quantum dynamics in the molecular frame to those in the laboratory frame, providing a transparent link between computation and measurement. The formalism reveals that in any such experiment, the molecular frame dynamics vary for molecules in different orientations and that certain coherences which are potentially experimentally accessible are rejected by the orientation-averaged reduced vibronic density matrix. Instead, Molecular Angular Distribution Moments (MADMs) are introduced as a more accurate representation of experimentally accessible information. Furthermore, the formalism provides a clear definition of a molecular frame quantum tomography, and specifies the requirements to perform such a measurement enabling the experimental imaging of molecular frame vibronic dynamics. Successful completion of such a measurement fully characterizes the molecular frame quantum dynamics for a molecule at any orientation in the laboratory frame.

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