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

Abstract

AbstractThe cooperative effects of hydrogen bonding in small water clusters (H2O)n (n=3–6) have been studied by using the partition of the electronic energy in accordance with the interacting quantum atoms (IQA) approach. The IQA energy splitting is complemented by a topological analysis of the electron density (ρ(r)) compliant with the quantum theory of atoms‐in‐molecules (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 hydrogen bonding in small water clusters arise from a compromise between: 1) the deformation energy (i.e., the energy necessary to modify the electron density and the configuration of the nuclei of the isolated water molecules to those within the water clusters), and 2) the interaction energy (Eint) of these contorted molecules in (H2O)n. Whereas the magnitude of both deformation and interaction ener

Evelio Francisco Miguélez

Associate Professor

Associate Professor of Physical Chemistry at the University of Oviedo. Expert in the development and application of quantum chemical topology methods, IQA analysis, and electron correlation descriptors.