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Deactivation of I( 2 P 1/2 ) by CH 3 Cl, CH 2 Cl 2 , CHCl 3 , CCl 3 F, and CCl 4
Author(s) -
Chiappero Malisa S.,
Argüello Gustavo A.
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:11<799::aid-kin3>3.0.co;2-q
Subject(s) - chemistry , overtone , excited state , dipole , relaxation (psychology) , molecule , photochemistry , atomic physics , computational chemistry , organic chemistry , spectral line , astronomy , psychology , social psychology , physics
Collisional deactivation of I( 2 P 1/2 ) by the title compounds was investigated through the use of the time‐resolved atomic absorption of excited iodine atoms at 206.2 nm. Rate constants for atomic spin‐orbit relaxation by CH 3 Cl, CH 2 Cl 2 , CHCl 3 , CCl 3 F, and CCl 4 are 3.1±0.3×10 −13 , 1.28±0.08×10 −13 , 5.7±0.3×10 −14 , 3.9±0.4×10 −15 , and 2.3±0.3×10 −15 cm 3 molecule −1 s −1 , respectively, at room temperature (298 K). The higher efficiency observed for relaxation by CH 3 Cl, CH 2 Cl 2 , and CHCl 3 reveals a contribution in the deactivation process of the first overtone corresponding to the C(SINGLEBOND)H stretching of the deactivating molecule (which lies close to 7603 cm −1 ) as well as the number of the contributing modes and certain molecular properties such as the dipole moment. It is believed that, for these molecules, a quasi‐resonant ( E‐v , r , t ) energy transfer mechanism operates. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 799–803, 1998