Effect of helium nanoclusters on the spectroscopic properties of embedded SF₆: Ionization, excitation and vibration

Ionization and excitation energies, IR and Raman spectra of sulfur hexafluoride (SF₆), located inside helium (He) nanoclusters with different sizes (SF₆@He_n; n=20, 40, 60), were calculated. The effect of the cluster size on the spectroscopic properties of the SF₆ was investigated and found that the He_n-SF₆ interaction in the He clusters with large number of atoms is small so that the ionization and absorption energies of SF₆ are not affected while for small He nanoclusters the He_n-SF₆ interaction is more important. The effect of He_n-SF₆ interaction and deformation of the fragments on the photoelectron and absorption spectra of SF₆@He_n were separated theoretically and discussed in details. It was deduced that the effect of the cluster size on the IR and Raman vibrational frequencies of the SF₆ is negligible for the cluster size range considered in this work. Density functional theory (DFT) employing M06-2X functional and 6-31+G(df) basis set were used for optimizing the structures of SF₆@He_n. Symmetry adapted cluster-configuration interaction (SAC-CI) methodology, with the same basis set, were used to calculate the ionization and excitation energies of the SF₆@He_n structures. Using the calculated ionization and absorption energies and their intensities, the photoelectron and absorption spectra of the considered SF₆@He_n structures were simulated and compared with the experiment.