Abstract

The gas-phase core binding energies of NSF, NSF/sub 3/, and several compounds of the types NSF/sub 2/R and F/sub 2/SNR have been determined. Qualitative interpretation of the data shows that N(p..pi..) ..-->.. S(d..pi..) bonding is probably important in the NSF/sub 2/R compounds and in NSF/sub 3/, that the bonding of the sulfur atom in NSF is similar to that in SO/sub 2/, and that the nitrogen atom of NSF/sub 3/ is more negatively charged than that of NSF (in spite of a stronger N-S bond in NSF/sub 3/). Quantitative interpretation of the data for NSF and NSF/sub 3/, together with literature valence ionization potentials, shows that the HOMO of each molecule has principally nitrogen 2p character and is stabilized by interaction with a higher lying sulfur 3d orbital. The approximate atomic orbital contributions to the other molecuar orbitals of these molecules are deduced.

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