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Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH(2)OH and CD(2)OH). II. Velocity map imaging studies.
MedLine Citation:
PMID:  22380040     Owner:  NLM     Status:  In-Data-Review    
The dissociation of the hydroxymethyl radical, CH(2)OH, and its isotopolog, CD(2)OH, following excitation in the 4ν(1) region (OH stretch overtone, near 13 600 cm(-1)) was studied using sliced velocity map imaging. A new vibrational band near 13 660 cm(-1) arising from interaction with the antisymmetric CH stretch was discovered for CH(2)OH. In CD(2)OH dissociation, D atom products (correlated with CHDO) were detected, providing the first experimental evidence of isomerization in the CH(2)OH ↔ CH(3)O (CD(2)OH ↔ CHD(2)O) system. Analysis of the H (D) fragment kinetic energy distributions shows that the rovibrational state distributions in the formaldehyde cofragments are different for the OH bond fission and isomerization pathways. Isomerization is responsible for 10%-30% of dissociation events in all studied cases, and its contribution depends on the excited vibrational level of the radical. Accurate dissociation energies were determined: D(0)(CH(2)OH → CH(2)O + H) = 10 160 ± 70 cm(-1), D(0)(CD(2)OH → CD(2)O + H) = 10 135 ± 70 cm(-1), D(0)(CD(2)OH → CHDO + D) = 10 760 ± 60 cm(-1).
M Ryazanov; C Rodrigo; H Reisler
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  136     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2012 Feb 
Date Detail:
Created Date:  2012-03-02     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  084305     Citation Subset:  IM    
Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
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