The role of neutral defects in the structural chemistry of liquid water

For defective water associates with an extra hydrogen atom (n-defective associates), size and structure effects on ionization potentials compared to defectless (normal) associates of similar structures have been investigated by quantum chemical and molecular mechanics methods. The ionization potentials of small n defective water associates increase (from fractions of eV to 7 eV–8 eV) with the number of water molecules in the associate. These are most probably the source of a hydrated electron that are responsible for the ensuing equilibrium between all defects in liquid water: neutral n and p defects and ion defects (H _aq ⁺ , OH _aq ^– , e _aq ^– ). Delocalization of an odd electron in defective associates stabilizes the latter and promotes their recombinations, forming hydrated water molecules, hydrogen peroxide, and gaseous hydrogen. Structural instability of fullerene (H₂O)₂₀ relative to normal associates has been found. This compound is stabilized by the endo inclusion of a hydrogen atom, and exo fixation of the hydrogen atom gives rise to an extra source of hydrated electrons.Original Russian Text Copyright © 2004 by G. A. Domrachev, D. A. Selivanovskii, E. G. Domracheva, L. G. Domracheva, A. I. Lazarev, P. A. Stunzhas, S. F. Shishkanov, and V. L. VaksTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 670–677, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.