Path integral Monte Carlo study of CO2 solvation in 4He clusters

We present a finite temperature quantum mechanical study of the dynamical and structural properties of small (4)He(N)-CO(2) clusters (N< or =17) using a path integral Monte Carlo (PIMC) method. The simulations were based on a He-CO(2) interaction potential with explicit dependence on the asymmetric stretch of the CO(2) molecule obtained at the CCSD(T) level. The shift of the CO(2) antisymmetric stretching (nu(3)) band origin and effective rotational constant were calculated as a function of the cluster size. In excellent agreement with experimental observations, the CO(2) vibrational band origin shifts and rotational constant show a turnaround near N=5, corresponding to a donut structure with the He atoms in equatorial positions of the linear dopant molecule.