Sebastianelli Francesco, Elmatad Yael S, Jiang Hao, Bacić Zlatko
Department of Chemistry, New York University, New York, New York 10003, USA.
J Chem Phys. 2006 Oct 28;125(16):164313. doi: 10.1063/1.2363989.
We present a comprehensive theoretical study of the quantum solvation of the HF molecule by small clusters of the H2 isotopomers, p-H2, HD, and o-D2, with up to 13 hydrogen solvent molecules. This complements our earlier work on the HF-doped parahydrogen clusters [H. Jiang and Z. Bacic, J. Chem. Phys. 122, 244306 (2005)]. The ground-state properties of the clusters are calculated exactly using the diffusion Monte Carlo method. Detailed information is obtained regarding the size and isotopomer dependences of the energetics, vibrationally averaged structures, and their rigidity. The rigidity of these clusters is investigated further by analyzing the distributions of their principal moments of inertia from the diffusion Monte Carlo simulations. The clusters are found to be rather rigid, especially when compared with the pure parahydrogen clusters of the same size. Extensive comparison is made with the quantum Monte Carlo results for the CO-doped parahydrogen clusters and significant differences are observed in the size evolution of certain properties, notably the chemical potential.
我们对H₂同位素异构体（仲氢（p-H₂）、氘化氢（HD）和邻-重氢（o-D₂））的小团簇与HF分子的量子溶剂化进行了全面的理论研究，其中溶剂分子最多有13个氢分子。这补充了我们早期关于HF掺杂仲氢团簇的工作[H. Jiang和Z. Bacic，《化学物理杂志》122, 244306 (2005)]。使用扩散蒙特卡罗方法精确计算了团簇的基态性质。获得了关于能量学、振动平均结构及其刚性的大小和同位素异构体依赖性的详细信息。通过分析扩散蒙特卡罗模拟中它们的主惯性矩分布，进一步研究了这些团簇的刚性。发现这些团簇相当刚性，特别是与相同大小的纯仲氢团簇相比。与CO掺杂仲氢团簇的量子蒙特卡罗结果进行了广泛比较，在某些性质的大小演化中观察到显著差异，特别是化学势。
