Determination of Absolute Product Branching Ratios in Mass Spectrometric Experiments:  Detecting Acetyl Radicals at CH2CO

The paper describes a general method for determining absolute branching ratios in mass spectrometric experiments. The method overcomes the chronic obstacle that the daughter ion fragmentation pattern of radical products is usually unknown. We report the absolute product branching ratio for competing...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1996-03, Vol.100 (13), p.5200-5204
Main Authors: Kitchen, D. C, Myers, T. L, Butler, L. J
Format: Article
Language:English
Online Access:Get full text
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Summary:The paper describes a general method for determining absolute branching ratios in mass spectrometric experiments. The method overcomes the chronic obstacle that the daughter ion fragmentation pattern of radical products is usually unknown. We report the absolute product branching ratio for competing primary C−Cl and C−C bond fission in chloroacetone after excitation on the 1nπ* absorption band. To determine this branching ratio, acetyl chloride is used to calibrate the relative detection efficiency of acetyl radicals at the CH2CO+ daughter ion relative to Cl atoms at 35Cl+. We also calculate the daughter ion production probability for CH2CO+ formed from internally excited CH3CO radicals.
ISSN:0022-3654
1541-5740
DOI:10.1021/jp9536918