title: Microwave spectrum, r(0) structure, dipole moment, barrier to internal rotation, and Ab initio calculations for fluoromethylsilane.
abstract: The microwave spectra of seven isotopomers of fluoromethylsilane, CH(2)FSiH(3), in the ground vibrational state were measured and analyzed in the frequency range 18-40 GHz. The rotational and centrifugal distortion constants were evaluated by the least-squares treatment of the observed frequencies of a- and b-type R- and b-type Q-transitions. The values for the components of the dipole moment were obtained from the measurements of Stark effects from both a- and b-type transitions and the determined values are: |mu(a)| = 1.041(5), |mu(b)| = 1.311(6), and |mu(t)| = 1.674(4) D. Structural parameters have been determined and the heavy atom distances (r(0)) in Angstroms are: Si-C = 1.8942(57) and C-F = 1.4035(55) and the angle in degree, angleSiCF = 109.58(14). A semi-experimental r(e) structure was also determined from experimental ground state rotational constants and vibration-rotation constants derived from ab initio force fields. The internal torsional fundamental, SiH(3), was observed at 149.2 cm(-1) with two accompanying hot bands at 138.8 and 127.5 cm(-1). The barrier to internal rotation was obtained as 717.3(16) cm(-1) (2.051(46) kcal mol(-1)) by combining the analysis of the microwave A and E splittings and the torsional fundamental and hot band frequencies. Ab initio calculations have been carried out with full electron correlation by the second-order perturbation method with several different basis sets up to MP2/6-311+G(d,p) to obtain geometrical parameters, barriers to internal rotation, and centrifugal distortion constants. Adjusted r(0) structural parameters have been obtained by combining the ab initio MP2/6-311+G(d,p) predicted values with the determined rotational constants for the fluoride as well as with the previously reported microwave data for the chloro- and bromo- compounds. These experimental results are compared to the corresponding parameters for the carbon analogues.
authors.affiliation: Department of Chemistry, University of Missouri - Kansas City, Kansas City, Missouri 64110-2499, USA. durigj@umkc.edu
authors.forename: James R
authors.initials: JR
authors.lastname: Durig
authors.forename: Savitha S
authors.initials: SS
authors.lastname: Panikar
authors.forename: Peter
authors.initials: P
authors.lastname: Groner
authors.forename: Hossein
authors.initials: H
authors.lastname: Nanaie
authors.forename: Hans
authors.initials: H
authors.lastname: Bürger
authors.forename: Peter
authors.initials: P
authors.lastname: Moritz