Journal of Chemical Physics, Vol.104, No.2, 488-498, 1996
Fermi Resonances and Local Modes in Stibine, Sbh3 - A Fourier Interferometric and Laser Photoacoustic Study of the Overtone Spectrum
The third stretching overtone region of a natural sample of stibine, SbH3, has been studied with high resolution infrared spectroscopy and the fifth and the sixth overtone region with Ti:Sapphire ring laser intracavity photoacoustic spectroscopy. The third overtone consists of a local mode pair of bands (400A(1)/E) which have been rotationally assigned both for (SbH3)-Sb-121 and (SbH3)-Sb-123 With a vibration-rotation model based on rectilinear normal coordinates. The vibrational dependencies of the model parameters are explained well with a simple block diagonal vibrational model. An extension of the standard vibration-rotation model is used to show that the upper state rotational energy level structures of both isotopic species are close to the rotational structure of an asymmetric rotor. High resolution laser spectrum of the fifth overtone consisting of a local mode pair of bands (600A(1)/E) shows severe perturbations in the upper state rotational structure. The (510A(1)/E) and (700A(1)/E) bands have been recorded with low resolution. All experimentally known vibration-rotation band origins of (SbH3)-Sb-121 have been reproduced well with a curvilinear internal valence coordinate system based Fermi resonance local mode model. The potential energy surface obtained agrees well with recent ab initio results.
Keywords:ENERGY-LEVEL STRUCTURE;FAR-INFRARED-SPECTRUM;BAND SYSTEM;HYDROGEN-SULFIDE;SYMMETRICAL HYDRIDES;ROTATIONAL STRUCTURE;GROUND-STATE;RING LASER;LIMIT;MOLECULES