Infrared fluorescence observations of electronic to vibrational energy transfer from Cl* [3p5(2P12)] to SO2

✍ Scribed by David A. Dolson; Diana S. West

• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 644 KB
• Volume: 216
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(93)90091-e

✦ Synopsis

Collisional transfer of electronic energy from spin-orbit excited chlorine atoms, Cl* [ ~P'(~P,,~) ] (E=882 cm-'), to vibrational energy in SOz has been observed by time-resolved infrared fluorescence from the fundamental SOI stretching levels. The rate constant ( k la) for Cl* quenching by SO2 at 298 k 3 K was determined to be (1.8 k0.2) x lo-" cm3 molecule-' s-'. Cl' electronic-to-vibrational (E-V) excitation of the SO2 stretching modes (ZQ = 115 I cm-' and v,= 1361 cm-') establishes a Q/V, population ratio, 1.6 k 0.5, that is greater than the equilibrium value, 0.36, even though the E-V transfer is 2 10 cm-' more endoergic to excite vg. This mode specificity is consistent with the importance of the dipole matrix element to the E-V excitation pathway.