Effects of molecular rotation on densities in doped [sup 4]He clusters

Mehul V. Patel (1) , Alexandra Viel (1) , Francesco Paesani (1) , Patrick Huang (1) , K. Birgitta Whaley (1)

1 Kenneth S. Pitzer Center for Theoretical Chemistry

The effects of including rotational degrees of freedom on helium solvation densities in molecule-doped helium clusters are investigated for a variety of molecules. Helium densities and cluster energetics are calculated with diffusion Monte Carlo methods. The rotationally induced changes in the helium density distributions are examined and quantified with a theoretical estimator applicable to molecules of arbitrary symmetry. This analysis leads to a discussion of adiabatic following of molecular rotation in a solvating helium environment. We make a detailed comparative study of the effect of molecular rotation as a function of four impurity molecules with varying mass and symmetry: SF6, OCS, HCN, and benzene (C6H6). We find that even for the heaviest rotors, only a fraction of the solvating helium density adiabatically follows the molecular motion in the quantum ground state. For the lightest molecule, HCN, a negligible degree of adiabatic following is found. A discussion of the various definitions is presented to clarify the meaning of adiabatic following, and its applicability to dynamical models of quantum rotation in helium droplets is evaluated in light of the quantitative findings of incomplete adiabatic following established here.

Mots clés: Helium clusters; Quantum Monte Carlo; Quantum dynamics

Domaines: Chimie théorique et/ou physique; Chimie-Physique [physics.chem-ph]

Mehul V. Patel, Alexandra Viel, Francesco Paesani, Patrick Huang, K. Birgitta Whaley. Effects of molecular rotation on densities in doped [sup 4]He clusters. Journal of Chemical Physics, 2003, 118 (11), pp.5011-5027. ⟨10.1063/1.1545106⟩. ⟨hal-01118297⟩