Density functional calculations on Jahn-Teller effect of tetrachloromethane cation

✍ Scribed by J. M. Garcia de la Vega; B. Miguel; E. San Fabian

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 169 KB
• Volume: 61
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1997)61:3<533::aid-qua21>3.0.co;2-8

✦ Synopsis

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Density functional DF calculations of the tetrachloromethane cation and its most important competitive process, the formation of CCl q , were carried out to explain the 3 possible stability of CCl q . From results obtained with B-LYP and B-P86 methods, it is 4 Ž . possible to produce a slight Jahn᎐Teller JT effect for a C planar structure of the cation s type CCl ᎏClᎏCl q compatible with the experimental data obtained by electron-spin 2 resonance spectroscopy. A complex of C structure CCl q ᎏCl which is similar to the 3v 3 previous one found in CF q appears when symmetry-broken wave functions are used in 4 HF-LYP and HF-P86 methods. Depending of the DF method employed, either one of the w Ž . x minima C planar and C is the most stable and competes with the dissociation of the s 3 v molecular ion to give CCl q . The JT stabilization energy is smaller when the JT active 3 coordinates are considered. ᮊ 1997 John Wiley & Sons, Inc. 4 confirmed, according with earlier experiments, that the CCl q ion is produced with small intensities by 4 electron ionization of CCl . More recently, Kime et 4 w x w x q al. 3 and Hop et al. 4 obtained stable CCl ions 4 by electron impact. The CCl q radical cation was studied by RSE 4 spectroscopy at low temperatures by Muto et al.