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Density functional calculations on Jahn‐Teller effect of tetrachloromethane cation
Author(s) -
de la Vega J. M. Garcia,
Miguel B.,
San Fabian E.
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)61:3<533::aid-qua21>3.0.co;2-8
Subject(s) - chemistry , jahn–teller effect , dissociation (chemistry) , bond dissociation energy , density functional theory , ion , computational chemistry , planar , crystallography , organic chemistry , computer graphics (images) , computer science
Density functional (DF) calculations of the tetrachloromethane cation and its most important competitive process, the formation of CCl + 3 , were carried out to explain the possible stability of CCl + 4 . From results obtained with B‐LYP and B‐P86 methods, it is possible to produce a slight Jahn‐Teller (JT) effect for a C s planar structure of the cation type CCl 2 (SINGLE BOND)Cl(SINGLE BOND)Cl + compatible with the experimental data obtained by electron‐spin resonance spectroscopy. A complex of C 3v structure CCl + 3 (SINGLE BOND)Cl which is similar to the previous one found in CF + 4 appears when symmetry‐broken wave functions are used in HF‐LYP and HF‐P86 methods. Depending of the DF method employed, either one of the minima [ C s (planar) and C 3v ] is the most stable and competes with the dissociation of the molecular ion to give CCl + 3 . The JT stabilization energy is smaller when the JT active coordinates are considered. © 1997 John Wiley & Sons, Inc.