Structures, binding energies, and spin-spin coupling constants of geometric isomers of pnicogen homodimers (PHFX)2, X = F, Cl, CN, CH3, NC

Abstract

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to determine the structures and binding energies of homodimers (PHFX)(2) for X = F, Cl, CN, CH(3), and NC. Geometric isomers of these complexes with C(i) symmetry exist, which are differentiated in terms of the nature of the atoms (F-P···P-F, H-P···P-H, or A-P···P-A, with A being the atom of X directly bonded to P), which approach a nearly linear alignment. Of these, isomers having F-P···P-F linear are the most stable. Binding energies, intermolecular distances, and EOM-CCSD spin-spin coupling constants are sensitive to both the nature of X and the atoms that assume the linear alignment.