Spectrum of the hydroxyl radical

Abstract

The B2Σ+ → A2Σ+ and C2Σ+ → A2Σ+ systems of OH and OD were photographed at high resolution. The apparent dissociation energy D0(A2Σ+) is calculated to be (18 847 ± 15) cm−1 for OH and (19 263 ± 15) cm−1 for OD. An upper limit to D0(X2Π3/2) of OH is deduced to be (35 420 ± 15) cm−1. Evidence for a potential maximum in the B2Σ+ state, which is about 100 cm−1 larger than that in the A2Σ+ state, is presented.The broadening of the rotational lines in several bands of both systems has established a strong predissociation of the A2Σ+ state near ν = 5 in OH. The lifetime of these predissociated levels is ≈10−11 s. A definite identification of the predissociating state has not been possible.Newly-discovered vibrational levels in the C2Σ+ state have led to the following constants, in cm−1, of the OH radical in the C2Σ+ state:[Formula: see text]Rotational constants and spin splitting constants in the A2Σ+ and B2Σ+ states, more accurate than previously available, are presented.