Microwave spectra of the SiH4-H2O complex: A new sort of intermolecular interaction

Abstract

Microwave spectral patterns observed for the silane-water complex were found much different from those of the methane-water complex. The SiH4-H2O complex is likely to have a tightly bound structure. The effective rotational and centrifugal distortion constants: B = 3621.1193 (45) MHz and DJ = 49.84 (30) kHz led to the distance between the Si and O atoms in the complex to be 3.3 Å, much shorter than the C and O separation in the CH4-H2O of 3.7 Å, and to the silane-water stretching force constant and stretching frequency to be 2.88 N/m and 65 cm−1, respectively, which are to be compared with 1.52 N/m and 55 cm−1 of the CH4-H2O. The characteristic features of the spectra observed for the main species 28SiH4-H2O are common to those of isotopic species: 29SiH4-H2O, 30SiH4-H2O, 28SiH4-H218O, 28SiH4-D2O, 29SiH4-D2O, 30SiH4-D2O, 28SiH4-HDO, 29SiH4-HDO, 30SiH4-HDO, 28SiD4-H2O, 28SiD4-D2O, and 28SiD4-HDO. The observed spectra also indicate that the silane executes a threefold internal rotation about one of its four Si–H bonds, while the C2 symmetry axis of the water is bent away from the internal-rotation axis. An internal axis method analysis yielded an estimate of the internal-rotation potential barrier V3 to be 140 ± 50 cm−1, and those based on diagonalization of a principal axis method Hamiltonian matrix and on the extended internal axis method resulted in V3 ranging from 180 to 100 cm−1, depending on the isotopic species studied. All the measurements were done by using a pulsed nozzle Fourier transform microwave spectrometer, and the spectral assignments were made with the aid of the Stark effect, which yielded the dipole moment to be 1.730 (10) D. Transitions in higher energy states of the SiH4 internal rotation were observed, clearly resolved from the main lines, when the carrier gas was replaced from Ar to Ne.