High resolution vacuum ultraviolet emission spectrum of D2: The B′Σu+1→XΣg+1 band system

Abstract

In this work, we have extended our previous high resolution study of the vacuum ultraviolet emission spectrum of the D2 molecule [M. Roudjane, et al. J. Chem. Phys. 125, 214305 (2006)] up to 124.2 nm in order to investigate the B' 1Sigmau+-->X 1Sigmag+ band system. The analysis of the spectrum has been carried out by means of a complex spectrum visual identification code IDEN [V. I. Azarov, Phys. Scr. 44, 528 (1991); 48, 656, (1993)] and supported by theoretical calculations using ab initio data [L. Wolniewicz, J. Chem. Phys. 103, 1792 (1995); 99, 1851 (1993); G. Staszewska and L. Wolniewicz, J. Mol. Spectrosc. 212, 208 (2002); L. Wolniewicz and G. Staszewska, 220, 45 (2003)] which provided level energies and transition probabilities. More than 1480 new emission lines have been observed and 109 bands belonging to the B' 1Sigmau+-->X 1Sigmag+ system have been identified between 84.1 and 121.6 nm. Except for the upsilon'-0 bands that were reported in absorption [I. Dabrowski and G. Herzberg, Can. J. Phys. 52, 1110 (1974)], all the upsilon'-upsilon" bands are reported here for the first time. The analysis led to the determination of 111 rovibronic energy levels in the B' 1Sigmau+ state, of which 31 with higher rotational numbers J are new. Observed perturbations are accounted for through a set of coupled equations involving the four excited electronic states B 1Sigmau+, B' 1Sigmau+, C 1Piu, and D 1Piu and including nonadiabatic couplings. The solution of this set provides the percent contribution of these four states to each of the observed rovibronic level.