Journal of Chemical Physics, Vol.120, No.12, 5650-5656, 2004
First stretching overtone of BiH3: An extreme local-mode case for XH3-type molecule?
The first stretching overtone region of short-lived, formerly inaccessible BiH3 near 3405 cm-1 has been measured by Fourier-transform infrared spectroscopy with a resolution of 0.0066 cm-1. Only the 2nu(1)(A(1))/nu(1)+nu(3)(E) band system has been observed. Rotational analysis, with transitions reaching J(max)(')=14, has revealed almost perfect local-mode behavior for the upper states denoted as (200A(1)/E) in the local-mode notation. Ratios of vibration-rotation interaction parameters (q) over bar (eff)/alpha(eff)((BB)) and r(eff)/alpha(eff)((BC)), and the appropriate rotational constant differences, are in good agreement with theoretical local-mode limit values. A simple stretching vibrational model reproduces the observed vibrational term values well, and the potential parameters obtained are close to true values. (C) 2004 American Institute of Physics.