Paesani F, Zillich R E, Kwon Y, Whaley K B
Department of Chemistry and Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2005 May 8;122(18):181106. doi: 10.1063/1.1913552.
We present a detailed analysis of the rotational excitations of the linear OCS molecule solvated by a variable number of para-hydrogen molecules (9 < or = N < or = 17). The effective rotational constant extracted from the fit of the rotational energy levels decreases up to N = 13, indicating near-rigid coupling between OCS rotations and para-hydrogen motion. Departure from rigidity is instead seen for larger clusters with 14 < or = N < or = 17. Path-integral Monte Carlo calculations show that the N dependence of the effective rotational constant can be explained in terms of a partial superfluid response of para-hydrogen to rotations about an axis perpendicular to the OCS axis. Complete para-hydrogen superfluid response to rotations about the OCS axis is found for N > or = 10.
我们对由可变数量的对氢分子（9≤N≤17）溶剂化的线性OCS分子的转动激发进行了详细分析。从转动能级拟合中提取的有效转动常数在N = 13之前减小，这表明OCS转动与对氢运动之间存在近乎刚性的耦合。相反，对于14≤N≤17的较大团簇，可以看到偏离刚性的情况。路径积分蒙特卡罗计算表明，有效转动常数的N依赖性可以通过对氢对绕垂直于OCS轴的轴的转动的部分超流响应来解释。当N≥10时，发现对氢对绕OCS轴的转动有完全的超流响应。
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