Abstract
The microwave spectrum of 25SiF 3 11BF 2 has been studied in the frequency range 24—40 GHz. Analysis of the low V 6 barrier spectrum is complicated by the presence of the heavy SiF 3 top. A computer treatment has been developed based on an ISM as outlined by Wilson et al. A non-periodic Mathieu equation is solved to allow the rotational energy matrix to be set up. Torsional levels are specified by quantum numbers V and α = 0, ±, ±2 and 3. About 40 lines belonging to J = 8 → 9 through 13 → 14 transitions were assigned and analysed by the foregoing treatment. The barrier height was determined as V 6 = 1.9 ± 0.8 cal/mol. Rotational constants were determined to be A(BF 2) = 10373 ± 30, B = 1504.90 ± 0.05 and C = 1314.79 ± 0.03 MHz. These constants lead to an Si-B bond length significiantly larger than that expected for a single bond, a result consistent with the extremely low barrier value. Stark effect measurements, with an analysis severely complicated by internal rotation, give the dipole moment μ = 1.09 ± 0.05 D.
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