First High-Resolution Infrared Observation of the Symmetry-Forbidden nu(5) Band of (10)B(2)H(6)

Spectra of (10)B monoisotopic diborane, B(2)H(6), have been recorded at high resolution (2-3 x 10(-3) cm(-1)) by means of Fourier transform spectroscopy in the region 700-1300 cm(-1). A thorough analysis of the nu(18) a-type, nu(14) c-type, and nu(5) symmetry-forbidden band has been performed. Of particular interest are the results concerning the nu(5) symmetry-forbidden band, which is observed only because it borrows intensity through an a-type Coriolis interaction with the very strong nu(18) infrared band located approximately 350 cm(-1) higher in wavenumber. The nu(5) band has been observed around 833 cm(-1) and consists of a well-resolved Q branch accompanied by weaker P- and R-branch lines. Very anomalous line intensities are seen, with the low K(a) transitions being vanishingly weak, and Raman-like selection rules observed. The determination of the upper state Hamiltonian constants proved to be difficult since the corresponding energy levels of each of the bands are strongly perturbed by nearby dark states. To account for these strong localized resonances, it was necessary to introduce the relevant interacting terms in the Hamiltonian. As a result the upper state energy levels were calculated satisfactorily, and precise vibrational energies and rotational and coupling constants were determined. In particular the following band centers were derived: nu(0) (nu(5)) = 832.8496(70) cm(-1), nu(0) (nu(14)) = 977.57843(70) cm(-1), and nu(0) (nu(18)) = 1178.6346(40) cm(-1). (Type A standard uncertainties (1varsigma) are given in parentheses.) Copyright 2000 Academic Press.