Theoretical investigation of hydrogen bonding interaction in H3O+(H2O)9 complex

Abstract

Hydrogen bonding interaction of hydronium ion with water molecules in its first and second solvation shell is studied using density functional theory with B3LYP functional and aug-cc-pvtz basis set. The nature of interaction and contribution from various interaction energies to the binding energy of a complex is studied using many-body analysis approach. The hydrogen bonds between hydronium and water molecules in its first solvation shell are stronger than those between water molecules in its second solvation shell. Many-body analysis shows that not only two-body but higher many-body energies up to seven-body interactions are also not negligible whereas eight-, nine-, and ten-body interaction energies are negligible for this complex. The terms containing hydronium ion as one of the many-body components have higher contribution to the respective total many-body interaction energy than those from the terms containing only water molecules. Additive as well as non-additive interactions are attractive and contribute about 58.6 and 44.3% respectively to the binding energy of a complex.

Assessing Many-Body Effects of Water Self-Ions. I: OH–(H2O)n Clusters

“…It is known that for systems whose MBEs converge quickly knowledge about molecular clusters can be systematically extended to bulk systems. Many studies have been reported in the literature investigating OH – (H 2 O) n and H 3 O + (H 2 O) n clusters using both theoretical − and experimental ,,− approaches. However, a rather small fraction of the theoretical work investigated many-body effects in these clusters. ,,,,,,− As a first step toward a quantitative assessment of many-body effects of water self-ions in aqueous systems, we report here an analysis of OH – –water interactions in low-energy isomers of OH – (H 2 O) n clusters, with n ≤ 5.…”

New equation for calculating total interaction energy in one noncyclic ABC triad and new insights into cooperativity of noncovalent bonds

“…Along with the interest in cooperativity in triads based on comparison of stabilization energies of triad and corresponding dyads the total interaction energy of a triad and pairwise interaction energies into its structure have been also studied using many‐body interaction energy (MBIE) approach . According to MBIE in an ABC triad the total interaction energy is given with following simplified equation: …”