Predissociation and spectroscopy of the 3A2(000) state of 18O3 from CRDS spectra of the 3A2(000)←X1A1(110) hot band near 7900 cm-1

The spectroscopy and predissociation of the (3)A(2)(0 0 0) state of O-18(3) are investigated from the analysis of the absorption spectrum of the (3)A(2)(0 0 0)<-(X) over tilde (1) A(1)(1 1 0) hot band recorded by high sensitivity cw-CRDS between 7600 and 7920 cm(-1). The noise equivalent absorption of the recordings is on the order of 1 x 10(-10) cm(-1). Forty transitions could be rotationally assigned and their line positions were used to derive approximate spectroscopic parameters of the (3)A(2)(0 0 0) upper state. Most of the transitions exhibit a clear broadening due to the predissociation of the (3)A(2)(0 0 0) upper state at 9573.61 cm(-1). The width of the Lorentzian component (from 0.02 up to more than 0.5 cm(-1)) was retrieved for some of the assigned transitions. The variation of the corresponding predissociation rates is due to the dependence of the spin-orbit coupling between the (3)A(2)(0 0 0) level and high lying dissociative vibrational levels of the (X) over tilde (1)A(1) electronic ground state, with (i) the J and K-a rotational quantum numbers and (ii) the energy gap between the coupled pair of rotational levels. From the predicted energies of the (X) over tilde (1)A(1) vibrational states and their vibrational overlap with the (3)A(2)(0 0 0) state, a few of these (X) over tilde (1)A(1) vibrational levels are identified as possibly responsible for the (3)A(2)(0 0 0) predissociation. The predissociative mechanism in O-18(3) is compared to that taking place in O-16(3). (C) 2012 Elsevier Ltd. All rights reserved.