Threshold photoelectron-photoion coincidence spectroscopy:: Dissociation dynamics and thermochemistry of Ge(CH3)4, Ge(CH3)3Cl, and Ge(CH3)3Br

被引：8
|
作者：
Dávalos, JZ
Koizumi, H
Baer, T [1 ]
机构：
[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
[2] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain
来源：
JOURNAL OF PHYSICAL CHEMISTRY A | 2006年 / 110卷 / 15期
关键词：
D O I：
10.1021/jp060264t
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：
Threshold photoelectron-photoion coincidence spectroscopy (TPEPICO) has been used to investigate the gas-phase ionic dissociation energies and thermochernistry of Me4Ge and Me3GeX, (Me = methyl; X = Cl, Br) molecules. The 0 K dissociation onsets for these species have been measured from the breakdown diagram and the ion time-of-flight distributions, which were modeled with the statistical RRKM theory and DFT calculations. The measured 0 K dissociative photoionization onsets were as follows: Me3Ge1 + Me (9.826 +/- 0.010 eV); Me3Ge+ + Cl (10.796 +/- 0.040 eV); Me(3)G(+) + Br (10.250 +/- 0.011 eV); Me2GeCl+ + Me (10.402 +/- 0.010 eV); and Me2GeBr+ + Me (10.333 +/- 0.020 eV). These onsets were used to obtain new values for Delta(f)H degrees(298) (in kJ/mol) of the neutral molecules Me3GeC+ (-239.8 +/- 5.7) and Me3GeBr (-196.5 +/- 4.3), and also for the following ionic species: Me3Ge+ (682.3 +/- 4.1), Me2GeCl+ (621.1 +/- 5.8), and Me2GeBr+ (657.8 +/- 4.7).
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页码：5032 / 5037
页数：6
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