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RESEARCH PRODUCT

Hydrogen-Bond Cooperative Effects in Small Cyclic Water Clusters as Revealed by the Interacting Quantum Atoms Approach

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The cooperative effects of hydrogen bonding in small water clus- ters (H2O)n (n = 3-6) have been studied by using the partition of the electronic energy in accordance with the interact- ing quantum atoms (IQA) approach. The IQA energy splitting is comple- mented by a topological analysis of the electron density (1(r)) compliant with the quantum theory of atoms-in-mole- cules (QTAIM) and the calculation of electrostatic interactions by using one- and two-electron integrals, thereby avoiding convergence issues inherent to a multipolar expansion. The results show that the cooperative effects of hy- drogen bonding in small water clusters arise from a compromise between: 1) the deformation energy (i.e., the energy necessary to modify the elec- tron density and the configuration of the nuclei of the isolated water mole- cules to those within the water clus- ters), and 2) the interaction energy (Eint) of these contorted molecules in (H2O)n. Whereas the magnitude of both deformation and interaction ener- gies is enhanced as water molecules are added to the system, the augmentation of the latter becomes dominant when the size of the cluster is increased. In addition, the electrostatic, classic, and exchange components of Eint for a pair of water molecules in the cluster (H2O)n� 1 become more attractive when a new H2O unit is incorporated to gen- erate the system (H2O)n with the last- mentioned contribution being consist- A the most important part of Eint throughout the hydrogen bonds under consideration. This is opposed to the traditional view, which regards hydro- gen bonding in water as an electrostati- cally driven interaction. Overall, the trends of the delocalization indices, dAW,W'), the QTAIM atomic charges, the topology of 1(r), and the IQA re- sults altogether show how polarization, charge transfer, electrostatics, and co- valency contribute to the cooperative effects of hydrogen bonding in small water clusters. It is our hope that the analysis presented in this paper could offer insight into the different intra- and intermolecular interactions present in hydrogen-bonded systems.