Phosphorous bonding in PCl3:H2O adducts: A matrix isolation infrared and ab initio computational studies

Non-covalent interaction between PCl 3 and H 2 O was studied using matrix isolation infrared spectroscopy and ab initio computations. Computations indicated that the adducts are stabilized through novel P⋯O type phosphorus bonding and conventional P Cl⋯H type hydrogen bonding interactions, where the former adduct is the global minimum. Experimentally, the P⋯O phosphorus bonded adduct was identified in N 2 matrix, which was evidenced from the shifts in the vibrational wavenumbers of the modes involving PCl 3 and H 2 O sub-molecules. Atoms in Molecules and Natural Bond Orbital analyses have been performed to understand the nature of interactions in the phosphorus and hydrogen bonded adducts. Interestingly, experimental evidence for the formation of higher PCl 3 H 2 O adduct was also observed in N 2 matrix.