2011
DOI: 10.1063/1.3549139
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Abstract: Analysis by kinetic modeling of the temperature dependence of thermal electron attachment to CF3Br J. Chem. Phys. 137, 024303 (2012) Electron attachment to POCl 3 was studied in the bath gas He over the pressure range 0.4-3.1 Torr and the temperature range 300-1210 K. Branching fractions of POCl 3 − , POCl 2 − , Cl − , and Cl 2 − were measured. The results are analyzed by kinetic modeling, using electron attachment theory for the characterization of the nonthermal energy distribution of the excited POCl 3 −* a… Show more

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Cited by 24 publications
(24 citation statements)
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References 32 publications
(52 reference statements)
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“…3,39 Here, we employ the modeling in the somewhat simplified form described above to fit the observed temperature dependences of attachment rate coefficients using two adjustable parameters, c 1 and E n,0 , in order to show that all results are consistent with the assumptions made in the kinetic modeling (i.e., good fits can be obtained with parameters remaining within physically reasonable bounds). Similarly, we show that the observed branching fractions and nearly flat temperature dependences of Br − and Br 2 − in attachment to the dibromide compounds are explicable within the framework of the kinetic modeling.…”
Section: Kinetic Modelingmentioning
confidence: 94%
See 1 more Smart Citation
“…3,39 Here, we employ the modeling in the somewhat simplified form described above to fit the observed temperature dependences of attachment rate coefficients using two adjustable parameters, c 1 and E n,0 , in order to show that all results are consistent with the assumptions made in the kinetic modeling (i.e., good fits can be obtained with parameters remaining within physically reasonable bounds). Similarly, we show that the observed branching fractions and nearly flat temperature dependences of Br − and Br 2 − in attachment to the dibromide compounds are explicable within the framework of the kinetic modeling.…”
Section: Kinetic Modelingmentioning
confidence: 94%
“…The SSACM methodology has been shown to reproduce experimental rate curves for homolytic bond cleavage of ionic species, 36 and may not be strictly appropriate for the Br 2 − eliminations which may pass through a discrete transition state. However, for small values of c SSACM , such as fit the data, the SSACM rate curves quickly approach limits 39,41 equivalent to a Rice-Ramsperger-Kassel-Marcus 37 rate curve. In any case, it appears clear that the flat experimental branching fractions for three of these systems can be explained by statistical dissociation from a metastable species, and therefore fit within the framework of the kinetic modeling.…”
Section: Product Branchingmentioning
confidence: 97%
“…11,14 We define all chemistry that might occur, as defined by the set of exothermic processes involving all species observed (i.e., ions) or inferred to be present in the flow tube. A set of rate constants for all reactions are guessed via a Monte Carlo procedure within constraints set either by known values in the literature or limited by calculated collision rate constants.…”
Section: Methodsmentioning
confidence: 99%
“…The technique, dubbed variable electron and neutral density attachment mass spectrometry (VENDAMS), 11 has been applied to measure rate constants and product distributions of mutual neutralization [12][13][14][15][16] and electron attachment to short-lived species such as radicals. 11,17,18 Here, a variation of the technique is used to determine thermal DR rate constants.…”
Section: Introductionmentioning
confidence: 99%
“…67 The disadvantage of this method is that while found to be valid at low energies, it may give unphysical behaviour at higher ion internal energies giving a rate curve with a negative slope. 68 The final theory to be mentioned is variational transition state theory (VTST). This theory is centred on finding the entropic minimum.…”
Section: B3 Unimolecular Rate Theoriesmentioning
confidence: 99%