Theoretical study of the relative stabilities of H+(X)2 and H+(X)3 conformers and their clustering energies: X CO and N2

✍ Scribed by Shigeru Ikuta

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 483 KB
• Volume: 6
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540060206

✦ Synopsis

Third-order Mgller-Plesset perturbation theory (MP3) with a 6-31G** basis set was applied to study the relative stabilities of H+(X)2 conformations (X =CO and N2) and their clustering energies. The effect of both basis set extensions and electron correlation is not negligible on the relative stabilities of the H+(COh clusters. The most stable conformation of H'(C0I2 is found to be a C , , structure in which a carbon atom of CO bonds to the proton of H+(CO), whereas that of H+(N2I2 is a symmetry Dmh structure. The second lowest energy conformations of H+(C0I2 and H+(N2)2 lie within 2 kcal/mol above the energies of the most stable structures. Clustering energies computed using MP3 method with the 6-31G** basis set are in good agreement with the experimental findings of Hiraoka, Saluja, and Kebarle. The low-lying singlet conformations of H+(X), (X = CO and N2) have been studied by the use of the Hartree-Fock MO method with the 6-31G** basis set and second-order Mgller-Plesset perturbation theory with a 4-31G basis set. The most stable structure is a T-shaped structure in which a carbon atom of CO (or a nitrogen atom of Nz) attacks the proton of the most stable conformation of H+(Xh clusters.