Electronic spectra and predissociation of jet-cooled CH3O and CH3O-Ar in the Ã2A1 state

Rovibronic analysis of the laser induced fluorescence excitation spectrum of the jet-cooled methoxy radical

“…Although this structure has been seen in many of the other studies on methoxy 12,14,15,20 there is some disagreement in the literature as to which of these components can be better Table II). …”

“…Experimentally, the radical can be conveniently studied by a variety of optical techniques for which the strong oscillator strength of the transition from the ground state to the first excited state ( A 2 A 1 ↔ X 2 E) lends itself well to laser induced fluorescence [8][9][10][11][12][13][14][15][16][17][18] (LIF) and dispersed fluorescence (and emission) 10,12,13,16,[18][19][20][21] and more recently stimulated emission pumping (SEP) studies. 22 Such experiments have led to considerable knowledge about the vibrational frequencies in the ground and excited electronic states.…”

“…Various jet expansion studies [9][10][11][12]14,15,18,20 have been performed over the past 15 years and a number of the vibrational frequencies have been determined for the A excited state but there have also been some problems associated with these studies. For a considerable time, even the frequency of the origin of the electronic transition was under dispute with a variety of values reported in the literature (for more information see Foster et al 12 ).…”

Vibronic structure of alkoxy radicals via photoelectron spectroscopy

“…Furthermore, there was no indication of any Jahn-Teller effects that would be expected as a result of both the electronic degeneracy of the 2 E ground state and the high-symmetry C 3v configuration. Supersonic expansion of the sample in laser-induced fluorescence ͑LIF͒ experiments significantly clarified the spectral features, [10][11][12][13][14] permitting the first direct observation of Jahn-Teller activity in methoxy radical. 15 However, it was only within the past several years that the advent of improved resolution techniques in conjunction with supersonic expansions allowed the biggest step toward understanding the spectroscopy of methoxy radical.…”

Photofragmentation dynamics of the thiomethoxy radical

“…The CH 3 S radical is a member of the methoxy family, which includes the methoxy radical CH 3 O, itself, as well as CF 3 O and CF 3 S. Methoxy has been the subject of many studies, both theoretical [1][2][3][4][5][6][7] and experimental [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] , as have CF 3 S 20,28,29 and CF 3 O, 29,30 albeit to a lesser extent. In recent studies 20,31 by our group the photofragmentation dynamics of CH(D) 3 O and CF 3 S have been studied as a function of energy and vibrational mode composition.…”