Semiclassical Molecular Dynamics in Extended Systems

V. Ara Apkarian得到了理论和 计算化学程序来执行半经典分子 扩展系统中量子动力学效应的动力学模拟。 这种方法已经被开发并成功地用于 气相光谱法该方法目前正应用于 低温固体、凝聚氢和氢键的光谱学 网络，以及室温液体共振拉曼和 光子回波光谱 量子效应是用一个“黑”来模拟的。 框`仅取决于输入的势能参数。 由于 在这些应用中的许多自由度，计算非常 密集。 这部分是通过依靠短时间来弥补的 通过重复蒙特卡罗的波函数重建的传播 取样. 为了理解大型系统中的量子动力学， 三维，如液体和固体，新的模拟方法是 needed. 特别是在凝聚相光谱学中， 潜在的分子结构及其运动的可观测性 目前依赖于近似技术。 理论发展 旨在从微观上理解凝聚相光谱 是解释和设计实验的宝贵工具。

V. Ara Apkarian is suported by a grant from the Theoretical and Computational Chemistry Program to perform semiclassical molecular dynamics simulations of quantum dynamic effects in extended systems. This approach has already been developed and employed successfully for gas-phase spectroscopy. The methodology is now being applied to the spectroscopy of cryogenic solids, condensed hydrogen, and hydrogen-bonded networks, as well as room-temperature liquid resonance-Raman and photon-echo spectroscopies. Quantum effects are simulated with a `black box` dependent only on inputted potential energy parameters. Due to the many degrees of freedom in these applications, the computations are very intensive. This is partially remedied by relying on short-time propagation with wavefunction reconstruction through repeated Monte Carlo sampling. In order to understand quantum dynamics in systems of large dimensionality, such as liquids and solids, new simulation methods are needed. In condensed phase spectroscopy in particular, connecting observables to the underlying molecular structures and their motions currently relies on approximate techniques. Theoretical developments that aim toward a microscopic understanding of condensed phase spectra are invaluable tools in the interpretation and design of experiments.