Toward an improved understanding of the AsH2 free radical: laser spectroscopy, ab initio calculations, and normal coordinate analysis.

Spectra of the Ã(2)A(1)-X̃(2)B(1) transition of the jet-cooled AsD(2) and AsHD isotopologues of the arsino radical have been studied by laser induced fluorescence and wavelength resolved emission techniques. A high-resolution spectrum of the AsD(2) 0(0)(0) band has been recorded, and an improved r(0) structure [r(0)(') = 1.487(4) Å, θ(0)(') = 123.

Heavy atom nitroxyl radicals. V. An experimental and ab initio study of the previously unknown H2PS free radical.

The B̃(2)A(')-X̃(2)A(') transition of the prototypical thiophosphoryl radical, H(2)PS, was observed for the first time using laser-induced fluorescence and single vibronic level emission spectroscopy. H(2)PS and its deuterated isotopologues, D(2)PS and HDPS, were produced in a pulsed supersonic discharge jet from a precursor mixture of Cl(3)PS and H(2) or D(2) or an H(2)/D(2) mixture in high-pressure argon. High level ab initio calculations of the lowest three doublet electronic states helped in the definitive assignment of the B̃-X̃ transition, which involves electron promotion from the π to the π∗ orbital.

Electronic spectroscopy of the jet-cooled arsenic dicarbide (C2As) free radical.

The (2)Delta(r)-X (2)Pi(r) band system of the jet-cooled arsenic dicarbide (C(2)As) free radical has been recorded by laser-induced fluorescence (LIF) techniques in the 685-588 nm region. The radical was produced in a pulsed electric discharge jet using a precursor mixture of AsCl(3) vapor and methane in high pressure argon. A series of weak bands involving all three excited state vibrations was observed for both (12)C(2)As and (13)C(2)As.