High-resolution infrared spectroscopy of Mg–HF and Mg–(HF)2 solvated in helium nanodroplets

Abstract

High-resolution infrared (IR) spectroscopy is used to investigate the Mg-HF and Mg-(HF)(2) van der Waals complexes. Both complexes are formed and probed within helium nanodroplets. Rotationally resolved zero-field and Stark spectra are assigned to a linear binary complex composed of a Mg atom bound to the hydrogen end of the HF molecule. Although high level ab initio calculations predict a fluorine bonded complex, none of the observed IR bands can be assigned to this complex. The collocation method is employed to determine the bound states on the two-dimensional intermolecular Mg-HF potential energy surface. The ground and first excited state wave functions for this potential surface have zero amplitude in the well corresponding to the fluorine bonded complex, consistent with experiment. The two HF stretching bands of the Mg-(HF)(2) complex are observed and assigned using a combination of the spectral symmetry, ab initio calculations, pick-up cell pressure dependencies, and dipole moment measurements. Comparisons with the helium solvated HF dimer show large changes to the HF stretching frequencies upon the addition of a single Mg atom to the hydrogen side of (HF)(2).