Transition from molecular complex to quantum solvation in OCS(He)_N

Abstract

We present quantum calculations of the rotational energy levels and spectroscopic rotational constants of the linear OCS molecule in variable size clusters of 4He, using spectral evolution quantum Monte Carlo methods that allow excited states to be accessed without nodal constraints. The rotational constants of OCS are found to decrease monotonically from the gas phase value as the number of helium atoms increases to N=6, after which the average constant increases to saturation at a value in excellent agreement with experimental measurements made on significantly larger clusters (N>1000). The minimum is shown to indicate a transition from a molecular complex to a quantum solvated molecule, with the former characterized by floppy but near rigid behavior, while the latter is characterized by non-zero permutation exchanges and a smaller extent of rigid coupling.