Journal of Chemical Physics, Vol.119, No.4, 1986-1995, 2003
Microscopic two-fluid theory of rotational constants of the OCS-H-2 complex in He-4 droplets
We present a microscopic quantum analysis for rotational constants of the OCS-H-2 complex in helium droplets using the local two-fluid theory in conjunction with path integral Monte Carlo simulations. Rotational constants are derived from effective moments of inertia calculated assuming that motion of the H-2 molecule and the local nonsuperfluid helium density is rigidly coupled to the molecular rotation of OCS and employing path integral methods to sample the corresponding H-2 and helium densities. The rigid coupling assumption for H-2-OCS is calibrated by comparison with exact calculations of the free OCS-H-2 complex. The presence of the H-2 molecule is found to induce a small local nonsuperfluid helium density in the second solvation shell which makes a non-negligible contribution to the moment of inertia of the complex in helium. The resulting moments of inertia for the OCS-H-2 complex embedded in a cluster of 63 helium atoms are found to be in good agreement with experimentally measured values in large helium droplets. Implications for analysis of rotational constants of larger complexes of OCS with multiple H-2 molecules in helium are discussed. (C) 2003 American Institute of Physics.