Electronic structure contribution to hydrogen bonding interaction of a   water dimer
  Hydrogen bond (H-bond) covalency has recently been observed in ice and liquid water, while the penetrating molecular orbitals (MOs) in the H-bond region of most typical water dimer system, (H2O)2, have also been discovered. However, obtaining the quantitative contribution of these MOs to the H-bond interaction is still problematic. In this work, we introduced the orbital-resolved electron density projected integral (EDPI) along the H-bond to approach this problem. The calculations show that, surprisingly, the electronic occupied orbital (HOMO-4) of (H2O)2 accounts for about 40% of the electron density at the bond critical point. Moreover, the charge transfer analysis visualizes the electron accumulating effect of the orbital interaction within the H-bond between water molecules, supporting its covalent-like character. Our work expands the classical understanding of H-bond with specific contributions from certain MOs, and will also advance further research into such covalency and offer quantitative electronic structure insights into intermolecular systems. 
Zhiyuan Zhang, Wanrun Jiang, Bo Wang, Zhigang Wang
physics.atm-clus physics.chem-ph