Experimental values of the rotational and vibrational constants of deuterated silyl fluoride

Abstract

ABSTRACTAccurate experimental values of the αA and αB rotation–vibration interaction, and ωi, xij and gij vibrational constants have been extracted from the most recent high-resolution Fourier transform infrared and millimetre-wave measurements in the spectra of the prolate symmetric top SiD3F, between 400 and 2000 cm−1. From the experimental values of the ground state rotational and rovibrational interaction parameters, accurate equilibrium rotational constants have been derived: Ae = 1.432326 (12) cm−1 and Be = 0.4112012 (45) cm−1 for silyl fluoride. The effective ground state structure has also been determined from the observed moments of inertia of SiD3F: r0(Si-D) = 1.4755 (29) Å; r0(Si-F) = 1.5931 (26) Å; θ0(DSiD) = 110.47 (32)° and θ0(DSiF) = 108.45 (56)°. A merge of equilibrium moments of 28SiH3F and 28SiD3F yielded an experimental equilibrium structure of silyl fluoride. This geometry has been found in good agreement with semi-experimental median values, as well as with the recent semi-experimental ab initio equilibrium structure obtained using all data available of the various isotopic species of silyl fluoride.