Threshold photoelectron photoion coincidence studies of parallel and sequential dissociation reactions

被引:82
作者
Baer, T
Sztáray, B
Kercher, JP
Lago, AF
Bödi, A
Skull, C
Palathinkal, D
机构
[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
[2] Eotvos Lorand Univ, Dept Gen & Inorgan Chem, H-1117 Budapest, Hungary
关键词
D O I
10.1039/b502051d
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
Recent advances in threshold photoelectron photoion coincidence (TPEPICO) make possible the analysis of several parallel and sequential dissociations of energy selected ions. The use of velocity focusing optics for the simultaneous collection of threshold and energetic electrons not only improves the resolution, but also permits subtraction of coincidences associated with "hot'' electrons, thereby yielding TPEPICO data with no contamination from "hot'' electrons. The data analysis takes into account the thermal energy distribution of the sample and uses statistical theory rate constants and energy partitioning in dissociation reactions to model the time of flight distributions and the breakdown diagram. Examples include CH(2)BrCl and P(C(2)H(5))(3). Of particular interest is the ability to extract error limits for rate constants and dissociation energies.
引用
收藏
页码:1507 / 1513
页数:7
相关论文
共 39 条
[1]   THE DISSOCIATION DYNAMICS OF STATE SELECTED METASTABLE ANILINE IONS BY SINGLE AND MULTI-PHOTON IONIZATION [J].
BAER, T ;
CARNEY, TE .
JOURNAL OF CHEMICAL PHYSICS, 1982, 76 (03) :1304-1308
[2]  
Baer T., 1986, ADV CHEM PHYS, V64, P111
[3]  
Baer T., 1996, UNIMOLECULAR REACTIO
[4]   On the parallel mechanism of the dissociation of energy-selected P(CH3)3+ ions [J].
Bodi, A ;
Kercher, JP ;
Baer, T ;
Sztáray, B .
JOURNAL OF PHYSICAL CHEMISTRY B, 2005, 109 (17) :8393-8399
[5]   ENERGY AND TIME-DEPENDENCE OF THE DECAY PROCESSES OF TOLUENE MOLECULAR CATIONS [J].
BOMBACH, R ;
DANNACHER, J ;
STADELMANN, JP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (13) :4205-4211
[6]   THE RATES OF HCL LOSS FROM ENERGY-SELECTED ETHYLCHLORIDE IONS - A CASE OF TUNNELING THROUGH AN H-ATOM TRANSFER BARRIER [J].
BOOZE, JA ;
WEITZEL, KM ;
BAER, T .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (05) :3649-3656
[7]   UNIMOLECULAR DECOMPOSITION OF ENERGY-SELECTED ANISOLE IONS - BREAKDOWN GRAPH AND METASTABLE DECAY-RATES [J].
DAS, PR ;
GILMAN, JP ;
MEISELS, GG .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1986, 68 (1-2) :155-165
[8]   FRAGMENTATION OF ENERGY-SELECTED HEXACARBONYLCHROMIUM ION [J].
DAS, PR ;
NISHIMURA, T ;
MEISELS, GG .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (13) :2808-2812
[9]   Heats of formation of the acetyl radical and ion obtained by threshold photoelectron photoion coincidence [J].
Fogleman, EA ;
Koizumi, H ;
Kercher, JP ;
Sztáray, B ;
Baer, T .
JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (24) :5288-5294
[10]   CRITERION OF MINIMUM STATE DENSITY IN UNIMOLECULAR RATE THEORY - APPLICATION TO ETHANE DISSOCIATION [J].
HASE, WL .
JOURNAL OF CHEMICAL PHYSICS, 1976, 64 (06) :2442-2449