Hydrogen bonding interactions in PN•••HX complexes: DFT and ab initio studies of structure, properties and topology

Spin-restricted DFT (X3LYP and B3LYP) and ab initio (MP2(fc) and CCSD(fc)) calculations in conjunction with the Aug-CC-pVDZ and Aug-CC-pVTZ basis sets were performed on a series of hydrogen bonded complexes PN center dot center dot center dot HX (X = F, Cl, Br) to examine the variations of their equilibrium gas phase structures, energetic stabilities, electronic properties, and vibrational characteristics in their electronic ground states. In all cases the complexes were predicted to be stable with respect to the constituent monomers. The interaction energy (Delta E) calculated using a super-molecular model is found to be in this order: PN center dot center dot center dot HF > PN center dot center dot center dot HCl > PN center dot center dot center dot HBr in the series examined. Analysis of various physically meaningful contributions arising from the Kitaura-Morokuma (KM) and reduced variational space self-consistent-field (RVS-SCF) energy decomposition procedures shows that the electrostatic energy has significant contribution to the over-all interaction energy. Dipole moment enhancement (Delta mu) was observed in these complexes expected of predominant dipole-dipole electrostatic interaction and was found to follow the trend PN center dot center dot center dot HF > PN center dot center dot center dot HCl > PN center dot center dot center dot HBr at the CCSD level. However, the DFT (X3LYP and B3LYP) and MP2 levels less accurately determined these values (in this order HF < HCl < HBr). Examination of the harmonic vibrational modes reveals that the PN and HX bands exhibit characteristic blue-and red shifts with concomitant bond contraction and elongation, respectively, on hydrogen bond formation. The topological or critical point (CP) analysis using the static quantum theory of atoms in molecules (QTAIM) of Bader was considered to classify and to gain further insight into the nature of interaction existing in the monomers PN and HX, and between them on H-bond formation. It is found from the analysis of the electron density rho(c), the Laplacian of electron charge density Delta(2)rho(c), and the total energy density (H-c) at the critical points between the interatomic regions that the interaction N center dot center dot center dot H is indeed electrostatic in origin (rho(c) > 0, del(2)rho(c) > 0 and H-c > 0 at the BCP) whilst the bonds in PN (rho(c) > 0, del(2)rho(c) > 0 and H-c < 0) and HX ((rho(c) > 0, del(2)rho(c) < 0 and H-c < 0)) are predominantly covalent. A natural bond orbital (NBO) analysis of the second order perturbation energy lowering, E(2), caused by charge transfer mechanism shows that the interaction N center dot center dot center dot H is n(N) -> BD*(HX) delocalization.