Electronic spectroscopy, lifetimes, and barrier to linearity in the, A1B1←X1A1 system of dibromocarbene

Using an improved discharge recipe for the production of dibromocarbene (CBr2), we recently reassigned the electronic origin of the (A) over tilde B-1(1) <- (X) over tilde (1)A(1) system, based on an extensive data set of isotope shifts for the pure bending transitions [C. Tao, C. Mukarakate, D. Brusse, Y. Mishchenko, S. A. Reid, J. Mol. Spectrosc. 240 (2006) 139-140]. In this study, we report the complete analysis of the fluorescence excitation spectrum of the (A) over tilde B-1(1) <- (X) over tilde (1)A(1) system in the 525-650 nm region, obtained at a rotational temperature of similar to 10 K. A total of 32 cold bands involving the pure bending levels 2(0)(n) with n = 2-19 and combination bands 1(0)(1)2(0)(n) (n = 1-16) in the (A) over tilde B-1(1) <- (X) over tilde (1)A(l) system were observed; a number of these are reported here for the first time. Rotational analysis typically yielded A rotational constants and band origins for all three bromine isotopomers ((CBr2)-Br-79, (C79BrBr)-Br-81, (CBr2)-Br-81), and Dunham expansion fits yielded an extensive set of vibrational parameters for each. The isotope shifts are in good agreement with the product rule, and, when plotted vs. bending quantum number, the measured A constants follow a linear trend except for the highest bending levels, where an abrupt increase is observed, indicative of the approach to linearity. This is mirrored in the vibrational intervals, which also change abruptly in this region, and the estimated barrier height of similar to 18 800 cm(-1) above the vibrationless level of the (X) over tilde (1)A(1) state is in excellent agreement with the ab initio prediction of Sendt and Bacskay [K. Sendt, G.B. Bacskay, J. Chem. Phys. 112 (2000) 2227-2238]. We also report fluorescence lifetimes as a function of vibrational level and K'(a); the lifetimes decrease rapidly with energy, but display no dependence on K'(a) over the measured range. The implications of these results for understanding the excited state structure of this prototypical carbene are emphasized. (c) 2006 Elsevier Inc. All rights reserved.