A new noncovalent force: Comparison of P ... N interaction with hydrogen and halogen bonds

When PH3 is paired with NH3, the two molecules are oriented such that the P and N atoms face one another directly, without the intermediacy of a H atom. Quantum calculations indicate that this attraction is due in part to the transfer of electron density from the lone pair of the N atom to the sigma* antibond of a P-H covalent bond. Unlike a H-bond, the pertinent hydrogen is oriented about 180 degrees away from, instead of toward, the N, and the N lone pair overlaps with the lobe of the P-H sigma* orbital that is closest to the P. In contrast to halogen bonds, there is no requirement of a sigma-hole of positive electrostatic potential on the P atom, nor is it necessary for the two interacting atoms to be of differing potential. In fact, the two atoms can be identical, as the global minimum of the PH3 homodimer has the same structure, characterized by a P ... P attraction. Natural bond orbital analysis, energy decomposition, and visualization of total electron density shifts reveal other similarities and differences between the three sorts of molecular interaction. (c) 2011 American Institute of Physics. [doi:10.1063/1.3562209]