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Low‐lying states of SF 6 and SF 6 − : Electron affinity of SF 6 and electron detachment of SF 6 −
Author(s) -
Richman Kent W.,
Banerjee Ajit
Publication year - 1993
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/qua.560480868
Subject(s) - electron affinity (data page) , chemistry , complete active space , ion , electron , adiabatic process , atomic physics , configuration interaction , wave function , octahedron , ground state , computational chemistry , physics , excited state , molecule , density functional theory , thermodynamics , quantum mechanics , basis set , organic chemistry
Calculations have been performed on low‐lying states of SF 6 and SF 6 −at the complete active space multiconfiguration self‐consistent field ( CAS – MCSCF ) level. These calculations involved optimization of basis function exponents, particularly the f ‐functions on sulfur and their effect on the potential energies and the SF 6 electron affinity. The CAS – MCSCF calculations for the anion and neutral included 4,863 and 2,115 configuration functions, respectively. Octahedral and selected distorted geometries were considered. The ground‐state equilibrium geometries correspond to the octahedral configuration of SF 6 ( 1 A 1 g ), R(SF) = 1.56 Å, ω e = 776 cm −1 , and of the anion SF 6 − ( 2 A 1 g ), R(SF) = 1.70 Å, ω e = 558 cm −1 . The adiabatic and vertical electron affinities are found to be ‐0.63 and 1.8 eV, respectively. Electron autodetachment phenomena associated with the anion are also discussed and a possible mechanism for this process is presented. © 1993 John Wiley & Sons, Inc.