DOE OSTI2015
Rotationally resolved high-resolution fluorescence excitation spectra of the 0–0 band of the B{sup ~2}E{sup ′}←X{sup ~2}A{sub 2}{sup ′} transition of the {sup 15}N substituted nitrate radical were observed for the first time, by crossing a jet-cooled molecular beam and a single-mode dye laser beam at right angles. Several thousand rotational lines were detected in the 15 080–15 103 cm{sup −1} region. We observed the Zeeman splitting of intense lines up to 360 G in order to obtain secure rotational assignment. Two, nine, and seven rotational line pairs with 0.0248 cm{sup −1} spacing were assigned to the transitions from the X{sup ~2}A{sub 2}{sup ′} (υ″ = 0, k″ = 0, N″ = 1, J″ = 0.5 and 1.5) to the {sup 2}E{sub 3/2}{sup ′} (J′ = 1.5), {sup 2}E{sub 1/2}{sup ′} (J′ = 0.5), and {sup 2}E{sub 1/2}{sup ′} (J′ = 1.5) levels, respectively, based on the ground state combination differences and the Zeeman splitting patterns. The observed spectrum was complicated due to the vibronic coupling between the bright B{sup ~2}E{sup ′} (υ = 0) state and surrounding dark vibronic states. Some series of rotational lines other than those from the X{sup ~2}A{sub 2}{sup ′} (J = 0.5 and 1.5) levels were also assigned by the ground state combination differences and the observed Zeeman splitting. The rotational branch structures were identified, and the molecular constants of the B{sup ~2}E{sub 1/2}{sup ′} (υ = 0) state were estimated by a deperturbed analysis to be T{sub 0} = 15 098.20(4) cm{sup −1}, B = 0.4282(7) cm{sup −1}, and D{sub J} = 4 × 10{sup −4} cm{sup −1}. In the observed region, both the {sup 2}E{sub 1/2}{sup ′} and {sup 2}E{sub 3/2}{sup ′} spin-orbit components were identified, and the spin-orbit interaction constant of the B{sup ~2}E{sup ′} (υ = 0) state was estimated to be −12 cm{sup −1} as the lower limit.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗