High-resolution infrared measurements on HSOH: Analysis of the OH fundamental vibrational mode

Abstract

High-resolution infrared measurements of the OH-stretching mode of oxadisulfane, HSOH, at 3625 cm −1 have been recorded using a Bruker IFS 120 HR Fourier transform spectrometer. More than 1300 lines have been assigned to the ν (OH) fundamental vibration mode, which is a hybrid band showing a c -type perpendicular band and an a -type parallel band spectrum of an asymmetric rotor molecule. The splitting due to the torsional-tunneling has not been observed in this band. The band center position at 3625.59260(20) cm −1 as well as rotational and centrifugal distortion constants for the ν (OH) vibrational excited state have been obtained from a least-squares fit analysis of a semirigid rotor. In addition the α OH experimental vibration–rotation correction terms of the OH-stretching mode have been derived and compared to values used in an earlier semi-empirical calculation of the HSOH structure. All data are in very good agreement with high level ab initio calculations and confirm the assignment of an earlier matrix isolation spectrum at 3608 cm −1 to the ν (OH) fundamental mode.