Laser Transient Absorption Spectroscopy of Bromomethylene

We report the observation and assignment of new high-resolution spectra of the A1A" <-- X1A' transition of bromomethylene, HCBr, obtained by transient laser absorption spectroscopy at near-infrared wavelengths. The 2(1)0 band of HCBr (nu0 = 11 957 cm-1) and the 2(2)0 band of DCBr (nu0 = 12 349 cm-1) have been observed for both naturally occurring isotopes of bromine. The c-type rotational branches of the Ka = 0 <-- 1 subbands have been assigned in detail. Other subbands have been partially assigned, but their detailed rotational quantum number analysis has not yet proved possible. Their presence does, however, indicate that the molecule exhibits nonlinear rotational structure in these vibrational levels, in contrast to what was found for the A1A" (0, 2, 0) level of HCBr (nu0 = 12 786 cm-1) [B. C. Chang and T. J. Sears, J. Chem. Phys. 105, 2135-2140 (1996)]. Analysis of the rotational structure in the spectra reported here has required a reassessment of certain rotational assignments of that previous work. We now find that the lower singlet state is isolated; there is no evidence of triplet state perturbations. Rotational constants derived for the ground state of all the naturally occurring isotopomers were used to estimate structural parameters. A barrier to linearity for the A1A" state, 13 590 cm-1 above the zero point level of the ground X1A' state, is estimated. Copyright 1998 Academic Press.