Journal of Physical Chemistry A, Vol.112, No.5, 934-941, 2008
Experimental determination of energy disposal in the dissociative electron recombinations of CS2+ and HCS2+
Vibronic optical emissions from CS(A(1)Pi -> X-1 Sigma(+)) and CS(a(3)Pi -> X-1 Sigma(+)) transitions have been identified from dissociative recombination (DR) of CS2+ and HCS2+ plasmas. All of the spectra were taken in flowing afterglow plasmas using an optical monochromator in the UV-visible wavelength region of 180-800 nm. For the CS(A -> X) and CS(a -> X) emissions, the relative vibrational distributions have been calculated for v' < 5 and v' < 3 in both types of plasmas for the CS(A) and CS(a) states, respectively. Both recombining plasmas show a population inversion from the v' = 0 to v' = 1 level of the CS(A) state, similar to other observations of the CS(A) state populations, which were generated using two other energetic processes. The possibility of spectroscopic cascading is addressed, such that transitions from upper level electronic states into the CS(A) and CS(a) states would affect the relative vibrational distribution, and there is no spectroscopic evidence supporting the cascading effect. Additionally, excited-state transitions from neutral sulfur (S(S-5(2)0 -> P-3(2)) and S(S-5(2)0 -> 3P(1))) and the products of ion-molecule reactions (CS(B-1 Sigma(+) -> A(1)Pi), CS+(B-2 Sigma(+) -> A(2)Pi(i)), and CS2+ ((A) over tilde (2)Pi(u) -> X-2 Pi(g))) have been observed and are discussed.