Path integral molecular dynamics combined with discrete-variable-representation approach: the effect of solvation structures on vibrational spectra of Cl2 in helium clusters

The structures and vibrational frequencies of Cl2-helium clusters have been studied using the path integral molecular dynamics method combined with the discrete-variable-representation approach. It is found that the Cl2-helium clusters form clear shell structures comprised of rings around the Cl2 bond. The vibrational frequencies calculated show a monotonically increasing red shift with an increase in cluster size. It can be concluded that the first solvation shell and its density around T-shaped configurations play the most important role in the observed frequency shifts.