Silyl halide radical anions

Abstract

Ab initio molecular orbital theory using diffuse-augmented basis sets and a second-order Møller–Plesset correction for electron correlation has been used to investigate the SiH₃F^–˙ and SiH₃Cl^–˙ radical anions. SiH₃F^–˙ is calculated not to be bound with respect to loss of an electron, whereas SiH₃Cl^–˙ is suggested to be bound at its minimum energy geometry, a C_s structure derived from a trigonal bipyramid, but not with respect to optimised SiH₃Cl. The thermodynamics and bonding in SiH₃Cl^–˙ are discussed and the performance of this level of theory for radical anions is assessed.