Collect. Czech. Chem. Commun. 2007, 72, 1122-1138

Gas-Phase Clustering of NO+ with H2S and H2O

Milan Uhlára and Ivan Černušákb,*

a Institute of Physics, Faculty of Art and Science, Silesian University, Bezručovo nám. 13, CZ-746 01 Opava 1, Czech Republic
b Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, SK-84215 Bratislava, Slovakia


The complex NO+·H2S, which is assumed to be an intermediate in acid rain formation, exhibits thermodynamic stability of ∆Hº300 = -76 kJ mol-1, or ∆Gº300 = -47 kJ mol-1. Its further transformation via H-transfer is associated with rather high barriers. One of the conceivable routes to lower the energy of the transition state is the action of additional solvent molecule(s) that can mediate proton transfer. We have studied several NO+·H2S structures with one or two additional water molecule(s) and have found stable structures (local minima), intermediates and saddle points for the three-body NO+·H2S·H2O and four-body NO+·H2S·(H2O)2 clusters. The hydrogen bonds network in the four-body cluster plays a crucial role in its conversion to thionitrous acid.

Keywords: Hydrogen bond; Hydration; Nitric oxide cation; Hydrogen sulfide; Quantum chemistry.

References: 37 live references.