Silane Radical Cation: A Theoretical Account on the Jahn–Teller Effect at a Triple Degeneracy

2013 ◽  
Vol 117 (36) ◽  
pp. 8794-8805 ◽  
Author(s):  
T. Mondal ◽  
A. J. C. Varandas
Keyword(s):  
Radical Cation ◽  
Teller Effect ◽  
Theoretical Account ◽  
Jahn Teller ◽  
Jahn Teller Effect

Description of Bond Pseudorotation, Bond Pseudolibration, and Ring Pseudoinversion Processes Caused by the Pseudo-Jahn–Teller Effect: Fluoro Derivatives of the Cyclopropane Radical Cation

2014 ◽  
Vol 67 (3) ◽  
pp. 435 ◽  
Author(s):  
Wenli Zou ◽  
Dieter Cremer
Keyword(s):  
Radical Cation ◽  
Positive Charge ◽  
Radical Cations ◽  
Molecular Geometry ◽  
Teller Effect ◽  
Curvilinear Coordinates ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Derivatives Of ◽  
Fluoro Derivatives

Curvilinear coordinates are used to describe the molecular geometry and the pseudo-Jahn–Teller surface of F-substituted cyclopropane radical cations using the equation-of-motion coupled cluster EOMIP-CCSD/cc-pVTZ approach. The monofluoro derivative 2 undergoes bond pseudolibration (incomplete bond pseudorotation) between two symmetry-equivalent biradicaloid forms separated by a barrier of 2.2 kcal mol–1 (1 kcal mol–1 = 4.186 kJ mol–1) at low temperature. Bond pseudorotation and ring pseudoinversion have barriers of 12.1 and 16.5 kcal mol–1 respectively. The relative energies of 2 are affected by the distribution of the positive charge in the C3 ring and the formation of a CF bond with partial π character. There is a change of the CF bond length from 1.285 to 1.338 Å along the bond pseudorotation path. The changes of the CF bond outweigh the deformation effects of the C3 ring; however, both are a result of the pseudo-Jahn–Teller effect according to an (A′ + A′′) ⊗ (a′ + a′′) interaction. For the pentafluoro derivative 3 of the cyclopropane radical cation, bond pseudorotation has a barrier of 16.3 kcal mol–1 whereas ring pseudoinversion is hindered by a barrier of 21.7 kcal mol–1. Radical cation 3 is the first example of a trimethylene radical cation.

Energy component analysis of the Jahn–Teller effect in the methane radical cation

1991 ◽  
Vol 94 (12) ◽  
pp. 8083-8088 ◽  
Author(s):  
Russell J. Boyd ◽  
Katherine Valenta Darvesh ◽  
Paul D. Fricker
Keyword(s):  
Radical Cation ◽  
Component Analysis ◽  
Teller Effect ◽  
Energy Component ◽  
Jahn Teller ◽  
Jahn Teller Effect
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