NON-EMPIRICAL CALCULATIONS ON THE CONFORMATION AND HYPERFINE-STRUCTURE OF THE SILYL RADICAL - INFLUENCE OF VIBRATIONAL EFFECTS

An ab-initio spin-restricted SCF and perturbative configuration interaction study of the silyl radical is presented. The vibrational dependence of isotropic coupling constants is investigated using double-zeta and double-zeta plus polarization basis sets. The calculations predict a nearly tetrahedral geometry for the radical with an inversion barrier of 5.85 kcal/mol. The vibrational treatment leads to coupling constants (αSi = -190.20 G;αH = +5.03 G) in excellent agreement with experiment. © 1979.