REACTIVE SCATTERING OF A SUPERSONIC FLUORINE-ATOM BEAM - F+C2H5I,C3H7I,(CH3)2CHI

被引:9
作者
HARKIN, JJ
JARVIS, RD
SMITH, DJ
GRICE, R
机构
[1] Chemistry Department, University of Manchester, Manchester
关键词
D O I
10.1080/00268979000101821
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Reactive scattering of F atoms with C2H5I, C3H7I and (CH3)2CHI molecules has been studied at an initial translational energy E 38kJmol-1 using a supersonic beam of F atoms seeded in He buffer gas. Centre-of-mass angular distributions of IF scattering show peaking in the forward and backward directions, which is consistent with reaction via persistent F—I—C2H5, F—I—C3H7 and F—I—CH(CH3)2 complexes with lifetimes greater than two rotational periods. The extended microcanonical theory indicates that the angular distribution of reactive scattering for F + C2H5I arises from a range of transition state configurations generated by internal rotation about the extended C—I bond. The reactive scattering for F + C3H7I arises from a wide range of transition-state configurations, with sharply peaked forward and backward scattering from extended configurations and mildly peaked scattering from more contracted configurations. However, the range of transition-state configurations is much more limited for F + (CH3)2CHI. This distinction confirms the persistence of significant C—I bonding, which restricts the rotation of the IF and C2H5, C3H7 or (CH3)2CH fragments in these product transition states. © 1990 Taylor and Francis Ltd.
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页码:323 / 344
页数:22
相关论文
共 26 条
[1]   STRUCTURE AND THERMODYNAMIC FUNCTIONS OF THE ISOPROPYL RADICAL - AN ABINITIO STUDY [J].
CHEN, YH ;
RAUK, A ;
TSCHUIKOWROUX, E .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (07) :2775-2777
[2]  
CHEUNG JT, 1973, FARADAY DISCUSS, V55, P377
[3]   QUANTUM-RESOLVED DYNAMICS OF EXCITED-STATES .4. RADIATIVE AND PRE-DISSOCIATIVE LIFETIMES OF IF B3-PI(0+) [J].
CLYNE, MAA ;
MCDERMID, IS .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1978, 74 :1644-1661
[4]  
ENTEMANN EA, 1967, DISCUSS FARADAY SOC, V44, P289
[5]   CROSSED MOLECULAR-BEAM STUDY OF F+CH3L [J].
FARRAR, JM ;
LEE, YT .
JOURNAL OF CHEMICAL PHYSICS, 1975, 63 (08) :3639-3648
[6]   REACTIVE SCATTERING OF A SUPERSONIC FLUORINE ATOM BEAM - F + ICI [J].
FIRTH, NC ;
SMITH, DJ ;
GRICE, R .
MOLECULAR PHYSICS, 1987, 61 (04) :859-867
[7]  
Fisk G. A., 1967, DISCUSS FARADAY SOC, V44, P228
[8]   MICROWAVE-DISCHARGE SOURCE FOR THE PRODUCTION OF SUPERSONIC ATOM AND FREE-RADICAL BEAMS [J].
GORRY, PA ;
GRICE, R .
JOURNAL OF PHYSICS E-SCIENTIFIC INSTRUMENTS, 1979, 12 (09) :857-860
[9]   PREFERRED TRANSITION-STATE GEOMETRY IN THE REACTION OF FLUORINE-ATOMS WITH IODOMETHANE MOLECULES [J].
JARVIS, RD ;
FIRTH, NC ;
SMITH, DJ ;
GRICE, R .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1990, 86 (11) :2059-2062
[10]   REACTIVE SCATTERING VIA A PERSISTENT COLLISION COMPLEX AS A FUNCTION OF IMPACT PARAMETER [J].
JARVIS, RD ;
HARKIN, JJ ;
SMITH, DJ ;
GRICE, R .
CHEMICAL PHYSICS LETTERS, 1990, 167 (1-2) :90-93