Ab initio molecular orbital calculations on NO+(H2O)(n) cluster ions. 2. Thermodynamic values for stepwise hydration and nitrous acid formation

Hammam, Essam, Lee, E.P.F. and Dyke, J.M. (2001) Ab initio molecular orbital calculations on NO+(H2O)(n) cluster ions. 2. Thermodynamic values for stepwise hydration and nitrous acid formation. Journal of Physical Chemistry A, 105 (23), 5528-5534. (doi:10.1021/jp003847q).

Abstract

Ab initio molecular orbital calculations have been used to compute thermodynamic constants (?H°, ?S°, ?G°) for the stepwise hydration reactions of NO+(H2O)(n), and for the competing rearrangement reaction which produces HONO and H+(H2O)(n) (for n less than or equal to 4). Geometry optimizations and harmonic frequency calculations were performed at the MP2/6-311++G(2d,p) level, and relative energies were computed at the MP2/augcc-pVTZ level with MP2/6-311++G(2d,p) optimized geometries. The geometry changes and energetics of these competing solvation and rearrangement reactions have been studied, and reasons are proposed to explain why NO+(H2O)(n+1) formation is the dominant process for n = 1 and n = 2 but HONO + H+(H2O)(n) formation contributes for n = 3 and becomes more important for n = 4.

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Contributors

Author: J.M. Dyke

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