OCS in small para-hydrogen clusters: energetics and structure with N=1-8 complexed hydrogen molecules

Abstract

We determine the structure and energetics of complexes of the linear OCS molecule with small numbers of para-hydrogen molecules, N=1-8, using zero temperature quantum Monte Carlo methods. Ground state calculations are carried out with importance-sampled rigid body diffusion Monte Carlo (IS-RBDMC) and excited state calculations with the projection operator imaginary time spectral evolution (POITSE) methodology. The ground states are found to be highly structured, with a gradual build up of two axial rings as N increases to 8. Analysis of the azimuthal density correlations around the OCS molecule shows that these rings are quite delocalized for small N values, but become strongly localized for N \geq 5 . Excited state calculations are made for a range of total cluster angular momentum values and the rotational energy levels fitted to obtain effective rotational and distortion constants of the complexed OCS molecule as a function of cluster size N. Detailed analysis of these spectroscopic constants indicates that the complexes of OCS with para-hydrogen have an unusually rich variation in dynamical behavior, with sizes N=1-2 showing near rigid behavior, sizes N=3-4 showing extremely floppy behavior, and the larger sizes N=5-8 showing more rigid behavior again. The large values of the distortion constant D obtained for N=3-4 are rationalized in terms of the coupling between the OCS rotations and the "breathing" mode of the first, partially filled ring of para-hydrogen molecules.