Potential energy surfaces and bound states for the open-shell van der Waals cluster Br–HF

Abstract

Semiempirical potential energy surfaces for the lowest three electronic states of the open-shell complex Br–HF are constructed, based on existing empirical potentials for Kr–HF and Kr–Ne and coupled-cluster electronic structure calculations for Br–Ne. Coupled cluster calculations are also described for He–F, Ne–F and Ar–F. Electrostatic interactions that arise from the quadrupole of the Br atom and the permanent multipoles of HF are also included in the Br–HF surfaces. The well depth of the lowest adiabatic surface is found to be 670 cm−1 at a linear equilibrium geometry. The results of helicity decoupled and full close-coupling calculations of the bound states of the complex are also described. The ground state, with total angular momentum projection quantum number |P|=3/2, is found 435 cm−1 below dissociation to Br (2P3/2)+HF (j=0). The lowest-frequency intermolecular bending and stretching vibrations are predicted around 145 and 211 cm−1, respectively. Parity splittings are found to be extremely small for bound states with projection quantum number |P|=3/2. The relevance of the results to recently recorded spectra of Br–HF is discussed.