Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5377237 | Chemical Physics | 2006 | 10 Pages |
Abstract
The optimization and spectral characteristics of the studied systems were carried out at the MP2 level of theory with 6-311++G(2d,2p) basis set. The performed calculations resulted in five stationary points on the PES for both trans and cis-HONO complexes. Two complexes are stabilized by the O-Hâ¯Ï bond, the other two by the O-Hâ¯Cl bond and one complex by the bifurcated, asymmetric Clâ¯Hâ¯Cl interaction. In one of the two complexes stabilized by the O-Hâ¯Cl hydrogen bond an additional C-Hâ¯O (for cis-HONO) or C-Hâ¯N (for trans-HONO) hydrogen bond also exists. The topological analysis of the distribution of the charge density by help of AIM theory confirmed the asymmetry of the Clâ¯Hâ¯Cl bifurcated hydrogen bond and the double O-Hâ¯Cl and C-Hâ¯O(N) interaction in one of the five structures. The values of the Ïb and â2Ïb indicate that the Clâ¯Hâ¯Cl bond is more asymmetric in the cis-HONO complex than in the trans-HONO one. The comparison of the experimental frequencies with the calculated ones for the five structures indicates that the trans- or cis-HONO complexes trapped in the matrixes correspond to the structures stabilized by the O-Hâ¯Ï bond or by the O-Hâ¯Cl bond.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Adriana Olbert-Majkut, Zofia Mielke,