The Cu*(2D5/2 and 2D3/2) chemiluminescent reactions with ClF

Abstract

The chemiluminescence from CuCl* and CuF* molecules formed by the reaction of metastable 2 D 3/2 and 2 D 5/2 copper atoms with ClF was studied at room temperature. The Cu* atoms were generated in a hollowcathode, flowing-afterglow reactor. A strong preference ($15:1) for production of electronically excited CuCl* over excited CuF* was found. Computer simulations of the observed spectra provided electronic branching ratios, as well as vibrational distributions within each CuCl* and CuF* electronic state. The vibrational energy disposal for CuCl*, h f v i ¼ 0.06-0.32, was similar to, or smaller than, the statistical value, whereas h f v i was much larger (%0.6) for the CuF* products. The total rate constants for the reaction of ground 2 S and metastable 2 D 5/2 and 2 D 3/2 states of Cu atoms with ClF were measured as 28 AE 3, 8.8 AE 2.5 and 10 AE 3 Â 10 À11 cm 3 molecule À1 s À1 . The highest observed CuF*(b 3 P 0 + ,1 ) vibrational levels from the ClF and F 2 reactions were used to recommend D 0 (CuF) ¼ 34 300 cm À1 . The results from ClF were compared with the data from the analogous F 2 , Cl 2 and Br 2 reactions. The branching fractions for chemiluminescent products decline in the order F 2 > Cl 2 > ClF > Br 2 , and the formation of CuX(X) from reactions of the Cu*( 2 D 5/2 and 2 D 3/2 ) atoms becomes more important in the series. The reactions of the ground and metastable-state copper atoms with SOCl 2 , CCl 4 and PCl 3 also are discussed.

Dissociation Energies of the Cu and Ag Monohalides and of Ni Monofluoride

“…In addition, Guido et al reported D ° 0 (CuCl) = 90.6 ± 1.1 kcal mol -1 , in accord with the value of 89.6 selected here and reported previously . And from the study of chemiluminescent reactions of excited Cu atoms with ClF, Sadeghi et al derived the value D ° 0 (CuF) = 98.1 kcal mol -1 , in fair agreement with the value 102.0 reported here. Aside from the studies noted here, we are not aware of any other experimental determinations of D ° 0 for the eight CuX/AgX monohalides under discussion.…”

Steric effect in the energy transfer reaction of Ar(P23)+N2

“…[23][24][25][26][27][28][29][30][31][32][33] From the + state preference of the product N 2 ͑C , 3 ⌸ u ͒, Setser et al 24 and Derouard et al 26 suggested that the energy transfer process proceeds via ArN 2 * complex formation. The energy transfer reaction of Ar͑ 3 P͒ +N 2 is one of the simplest reaction systems widely investigated so far.…”

Production yields of H(D) atoms in the reactions of N2(AΣu+3) with C2H2, C2H4, and their deuterated variants

“…[6][7][8] N 2 ͑A 3 ⌺ u + ͒ is often produced by the energy transfer from Ar͑4s 3 P 0,2 ͒ to N 2 in discharge-flow systems. [14][15][16][17] The energy levels of Xe͑6s͓3/2͔ 2 ͒ and Xe͑6sЈ͓1/2͔ 0 ͒ are lower than the dissocia-tion limit of N 2 , but still higher than those of N 2 ͑BЈ͒ and N 2 ͑W͒. However, the electronic energy of Ar͑4s 3 P 0,2 ͒ is higher than those of some metastable triplet states of molecular nitrogen, such as BЈ 3 ⌺ u − and W 3 ⌬ u , 13 and the production of these species may not be ignored.…”