화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.107, No.49, 10527-10532, 2003
Quenching of W(2P(1/2)) by Cl-2 and Cl atoms over the temperature range 297-663 K
Time-resolved fluorescence measurements have been used to examine the quenching of I(P-2(1/2)) by Cl-2 and Cl atoms. Pulsed photolysis of CF3I was used to generate I*. Quenching by Cl-2 was examined using 248 nm photolysis as Cl-2 does not absorb significantly at this wavelength. Photolysis at 308 nm, which dissociates both CF3I and Cl-2, was used to investigate quenching by Cl atoms. Quenching kinetics were characterized over the temperature range from 297 to 663 K. The rate constant for quenching by Cl atoms was found to be almost independent of temperature, whereas the rate constant for Cl-2 increased by 3 orders of magnitude in going from 297 to 663 K. Theoretical calculations show that quenching by Cl atoms is mediated by a curve crossing process. The temperature dependence of the Cl-2 quenching rate constant is attributed to the reactive channel I* + Cl-2 --> ICl + Cl(P-2).