Thermal energy reactions of CO2+ with chloromethanes

Article abstract of DOI:10.1063/1.466052

Rate constants and product ions have been determined for thermal energy reactions of CO2⁺ with CHnCl4-n (n = 0-3) by using an ion-beam apparatus.Total rate constants are (8.7+/-3.7), (6.7+/-3.1), (9.1+/-4.1), and (4.9+/-1.6)x10^-10 cm³ s^-1 for CH3Cl, CH2Cl2, CHCl3, and CCl4, respectively.These values amount to 38percent-61percent of the collision rate constants estimated from either the Langevin or averaged dipole oriented theory.Although charge transfer followed by the successive loss of a Cl atom is the major product channel, parent ions are formed from CH3Cl and CH2Cl2 with branching ratios of 33percent+/-5percent and 25percent+/-3percent, respectively.The reaction mechanisms are interpreted in terms of the electronic states of the parent molecular ion accessible in the charge-transfer processes.The lack of formation of parent ions from CHCl3 and CCl4 is explained as due to complete (pre)dissociation of ionic states below 13.78 eV.

Full text of DOI:10.1063/1.466052

Thermal energy reactions of CO+ 2 with chloromethanes
Masaharu Tsuji, Tsuyoshi Funatsu, Kenichi Matsumura, and Yukio Nishimura
Citation: The Journal of Chemical Physics 99, 4526 (1993); doi: 10.1063/1.466052
View online: http://dx.doi.org/10.1063/1.466052
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/99/6?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
128.42.202.150 On: Tue, 25 Nov 2014 07:36:30