Rabani Eran, Jortner Joshua
School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.
J Phys Chem B. 2006 Sep 28;110(38):18893-7. doi: 10.1021/jp057067z.
We applied the quantum path integral Monte Carlo method for the study of (para-H)N (N = 5-33) clusters at T = 2 K, exploring static and dynamic order, which originates from the effects of zero-point energy, kinetic energy, and thermal fluctuations in quantum clusters. Information on dynamic structure was inferred from the asymptotic tails of the cage correlation function calculated from the centroid Monte Carlo trajectory. The centroid cage correlation function decays to zero for large clusters (N = 15-33), manifesting the interchange of molecules between different solvation shells, with statistically diminishing back interchange. Further evidence for the floppiness of para-hydrogen clusters emerges from the Monte Carlo evolution of the centroid of a tagged molecule, which exhibits significant changes in the list of its first and second solvation shells due to the interchange of molecules between these shells.
我们应用量子路径积分蒙特卡罗方法研究了在T = 2 K时的(对-氢)N（N = 5 - 33）团簇，探索了源于量子团簇中零点能、动能和热涨落效应的静态和动态有序性。动态结构信息是从由质心蒙特卡罗轨迹计算出的笼状关联函数的渐近尾部推断出来的。对于大团簇（N = 15 - 33），质心笼状关联函数衰减至零，这表明不同溶剂化壳层之间分子的交换，且反向交换在统计上逐渐减少。对-氢团簇松软性的进一步证据来自于标记分子质心的蒙特卡罗演化，由于这些壳层之间分子的交换，其第一和第二溶剂化壳层列表显示出显著变化。
