DYNAMICS OF ETHYLENE PHOTODISSOCIATION FROM ROVIBRATIONAL AND TRANSLATIONAL ENERGY-DISTRIBUTION OF H-2 PRODUCTS

被引:84
作者
CROMWELL, EF [1 ]
STOLOW, A [1 ]
VRAKKING, MJJ [1 ]
LEE, YT [1 ]
机构
[1] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720
关键词
D O I
10.1063/1.462942
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
The dynamics of H-2 elimination from ethylene was studied via a pump and probe technique utilizing an ultrahigh resolution vacuum ultraviolet laser system. H-2 product internal and translational energy distributions were obtained for the photodissociation at 193 nm. The distribution of energy in H-2 product from the dissociation of (1,1)-dideuteroethylene is also presented. Two separate H-2 elimination channels are inferred: a 1,1 elimination producing the vinylidene radical and a 1,2 elimination producing the acetylene molecule. Differences between the vibrational, rotational, and translational energy distributions for these two channels are discussed and correlations between product internal and translational energy are presented. A comparison with ab initio calculations of the transition state configurations for these processes is made. We suggest that the H-2 elimination process may be nonstatistical in nature. The D atom elimination from C2D4 was examined and kinetic energy distribution for this product measured.
引用
收藏
页码:4029 / 4040
页数:12
相关论文
共 38 条
[31]   THE GROUND-STATE SINGLET POTENTIAL SURFACE FOR C2H4 [J].
RAGHAVACHARI, K ;
FRISCH, MJ ;
POPLE, JA ;
SCHLEYER, PV .
CHEMICAL PHYSICS LETTERS, 1982, 85 (02) :145-149
[32]   THE HYDROGEN-ATOM CHANNEL IN THE PHOTODISSOCIATION OF ETHYLENE [J].
SATYAPAL, S ;
JOHNSTON, GW ;
BERSOHN, R ;
OREF, I .
JOURNAL OF CHEMICAL PHYSICS, 1990, 93 (09) :6398-6402
[33]   MOLECULAR DETACHMENT PROCESSES IN VACUUM UV PHOTOLYSIS OF GASEOUS HYDROCARBONS .1. ETHYLENE .2. BUTANE [J].
SAUER, MC ;
DORFMAN, LM .
JOURNAL OF CHEMICAL PHYSICS, 1961, 35 (02) :497-&
[34]   THE DYNAMICS OF H-2 ELIMINATION FROM ETHYLENE [J].
STOLOW, A ;
BALKO, BA ;
CROMWELL, EF ;
ZHANG, JS ;
LEE, YT .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1992, 62 (03) :285-300
[35]   COMPACT VACUUM ULTRAVIOLET SOURCE FOR PHOTOELECTRON-SPECTROSCOPY [J].
TONKYN, RG ;
WHITE, MG .
REVIEW OF SCIENTIFIC INSTRUMENTS, 1989, 60 (07) :1245-1251
[36]   REACTIONS OF ETHYLIDENE IN VACUUM ULTRAVIOLET PHOTOLYSIS OF ETHYLENE [J].
TSCHUIKOWROUX, E ;
MCNESBY, JR ;
JACKSON, WM ;
FARIS, JL .
JOURNAL OF PHYSICAL CHEMISTRY, 1967, 71 (05) :1531-+
[37]   KINETIC AND INTERNAL ENERGY-DISTRIBUTIONS VIA VELOCITY-ALIGNED DOPPLER SPECTROSCOPY - THE 193 NM PHOTODISSOCIATION OF H2S AND HBR [J].
XU, Z ;
KOPLITZ, B ;
WITTIG, C .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (02) :1062-1069
[38]  
YOSHIMINE M, COMMUNICATION