Dynamics for the Cl+C2H6->HCl+C2H5 reaction examined through state-specific angular distributions

被引:86
作者
Kandel, SA
Rakitzis, TP
LevOn, T
Zare, RN
机构
[1] Department of Chemistry, Stanford University, Stanford
关键词
D O I
10.1063/1.472581
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
Photolysis of Cl-2 initiates the title reaction at a sharply defined collision energy of 0.24+/-0.03 eV. Nascent product rotational state distributions for HCl (v=0) are determined using resonance enhanced multiphoton ionization (REMPI), center-of-mass scattering distributions are measured by the core-extraction technique, and the average internal energy of the C2H5 product is deduced from the dependence of the core-extracted signal on the photolysis polarization. The HCl product has little rotational excitation, but the scattering distribution is nearly isotropic. Although seemingly contradictory, both of these features can be accounted for by using the simple line-of-centers model presented to explain earlier results for the Cl+CH4 reaction. in contrast to the Cl+CH4 reaction, the data suggest that the Cl+C2H6 reaction proceeds through a loosely constrained transition-state geometry. The reactions of atomic chlorine with ethane, C2H6, and perdeuteroethane, C2D6, yield virtually identical results. These findings, along with the low energy deposited by the reaction into the ethyl product (200+/-120 cm(-1)), demonstrate that the alkyl fragment acts largely as a spectator in this hydrogen abstraction reaction. (C) 1996 American Institute of Physics.
引用
收藏
页码:7550 / 7559
页数:10
相关论文
共 40 条
[21]  
ORREWING AJ, UNPUB J CHEM PHYS
[22]  
ORREWING AJ, 1995, CHEM DYNAMICS KINETI
[23]   CHEMICAL-DYNAMICS OF THE REACTION BETWEEN CHLORINE ATOMS AND DEUTERATED CYCLOHEXANE [J].
PARK, JH ;
LEE, YS ;
HERSHBERGER, JF ;
HOSSENLOPP, JM ;
FLYNN, GW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (01) :58-63
[24]   KINETICS AND THERMOCHEMISTRY OF THE REACTION C2D6+CL-REVERSIBLE-C2D5+DCL - THE HEAT OF FORMATION OF THE C2D5 AND C2H5 RADICALS [J].
PARMAR, SS ;
BENSON, SW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (01) :57-61
[25]  
Press W. H., 1986, NUMERICAL RECIPES
[26]   EXPERIMENTAL STUDIES AND THEORETICAL PREDICTIONS FOR THE H+D-2-]HD+D REACTION [J].
SCHNIEDER, L ;
SEEKAMPRAHN, K ;
BORKOWSKI, J ;
WREDE, E ;
WELGE, KH ;
AOIZ, FJ ;
BANARES, L ;
DMELLO, MJ ;
HERRERO, VJ ;
RABANOS, VS ;
WYATT, RE .
SCIENCE, 1995, 269 (5221) :207-210
[27]   BEYOND STATE-TO-STATE DIFFERENTIAL CROSS-SECTIONS - DETERMINATION OF PRODUCT POLARIZATION IN PHOTOINITIATED BIMOLECULAR REACTIONS [J].
SHAFERRAY, NE ;
ORREWING, AJ ;
ZARE, RN .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (19) :7591-7603
[28]   Picturing the transition-state region and understanding vibrational enhancement for the Cl+CH4->HCl+CH3 reaction [J].
Simpson, WR ;
Rakitzis, TP ;
Kandel, SA ;
LevOn, T ;
Zare, RN .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (19) :7938-7947
[29]   CORE EXTRACTION FOR MEASURING STATE-TO-STATE DIFFERENTIAL-CROSS SECTIONS OF BIMOLECULAR REACTIONS [J].
SIMPSON, WR ;
ORREWING, AJ ;
RAKITZIS, TP ;
KANDEL, SA ;
ZARE, RN .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (17) :7299-7312
[30]   REACTION OF CL WITH VIBRATIONALLY EXCITED CH4 AND CHD3 - STATE-TO-STATE DIFFERENTIAL CROSS-SECTIONS AND STERIC EFFECTS FOR THE HCL PRODUCT [J].
SIMPSON, WR ;
RAKITZIS, TP ;
KANDEL, SA ;
ORREWING, AJ ;
ZARE, RN .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (17) :7313-7335