Intermolecular Complexes of HXeOH with Water: Stabilization and Destabilization Effects

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• 作者：Alexander V. Nemukhin ; Bella L. Grigorenko ; Leonid Khriachtchev ; Hanna Tanskanen ; Mika Pettersson ; and Markku Rä ; sä ; nen
• 刊名：Journal of the American Chemical Society
• 出版年：2002
• 出版时间：September 11, 2002
• 年：2002
• 卷：124
• 期：36
• 页码：10706 - 10711
• 全文大小：171K
• 年卷期：v.124,no.36(September 11, 2002)
• ISSN：1520-5126

文摘

Theoretical and matrix-isolation studies of intermolecular complexes of HXeOH with watermolecules are presented. The structures and possible decomposition routes of the HXeOH-(H₂O)_n (n =0, 1, 2, 3) complexes are analyzed theoretically. It is concluded that the decay of these metastable speciesmay proceed through the bent transition states (TSs), leading to the global minima on the respective potentialenergy surfaces, Xe + (H₂O)_n+1. The respective barrier heights are 39.6, 26.6, 11.2, and 0.4 kcal/mol forn = 0, 1, 2, and 3. HXeOH in larger water clusters is computationally unstable with respect to the bendingcoordinate, representing the destabilization effect. Another decomposition channel of HXeOH-(H₂O)_n, viaa linear TS, leads to a direct break of the H-Xe bond of HXeOH. In this case, the attached water moleculesstabilize HXeOH by strengthening the H-Xe bond. Due to the stabilization, a large blue shift of the H-Xestretching mode upon complexation of HXeOH with water molecules is featured in calculations. On thebasis of this computational result, the IR absorption bands at 1681 and 1742 cm^-1 observed after UVphotolysis and annealing of multimeric H₂O/Xe matrixes are assigned to the HXeOH-H₂O and HXeOH-(H₂O)₂ complexes. These bands are blue-shifted by 103 and 164 cm^-1 from the known monomeric HXeOHabsorption.