Relativistic ab initio study on PtF and HePtF

Abstract

The electronic structures and spectroscopic constants of the first three low-lying electronic states (Ω = 1/2, 3/2, and 5/2) of the linear HePtF complex were investigated by highly accurate relativistic ab initio methods, in which the spin–orbit coupling was taken into account, and compared with the results of PtF. It shows that the complex is significantly different from the typical van der Waals systems because of short He–Pt bond distances (1.80∼1.87 Å), large He–Pt stretching frequencies (500∼600 cm⁻¹), considerable binding energies (1400∼2500 cm⁻¹ with corrections), and a small electron transfer from helium (about 0.06). However, the topological analysis of the electron density distribution indicates that there is strong van der Waals interaction in the He–Pt bond instead of weak covalent one.