Theoretical Investigations of the Nature of Interaction of ClF with HF, H2O, and NH3.

The interactions of the first-row hydrides (HF, H2O, and NH3) with ClF have been investigated by performing calculations at the second-order perturbation theory based on the Møller-Plesset partition of the Hamiltonian with the aug-cc-pVTZ basis set. The geometries and vibrational frequencies in the present study were obtained by carrying out explicit counterpoise-corrected optimization. In order to understand that the Cl-X-type (X = F, O, and N) structure is more stable than the corresponding hydrogen-bonded structure in these complexes, the electronic properties were also investigated. Furthermore, the symmetry-adapted perturbation theory calculations were performed to gain more insight into the nature of the hydrogen-bond and Cl-X-type interactions. The analysis of the interaction energy components indicates that, in contrast to the hydrogen-bonded complexes, the inductive and dispersive interaction is the most important term in the Cl-X-type complexes, as we progress from HF to NH3.