Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 132, Issue 3, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.3297892
Keywords
bonds (chemical); configuration interactions; dissociation energies; excited states; organic compounds; photodissociation; SCF calculations
Funding
- National Scholarship Foundation of the Chinese Ministry of Education
- NSFC [20720102038]
- Major State Basic Research Development Programs [2004CB719903]
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In this work, we studied the photodissociation dynamics of methyl formate (CH3OC(O)H) using state-of-the-art multireference configuration interaction with single and double excitation and the complete active space self-consistent field methods. It was found that the direct alpha-C - O bond cleavage in the first excited singlet state (S-1) is the dominant dissociation channel, consistent with the recent experiment [S. H. Lee, J. Chem. Phys. 129, 194304 (2008)]. This cleavage mechanism is different from that for aldehydes/ketones where it occurs in the lowest triplet state (T-1) as a result of the S-1 -> T-1 intersystem crossing. On the basis of comparison to the alpha-bond fission in the asymmetrically substituted aliphatic carbonyl compounds studied previously, we suggest the photolytic reaction of CH3OC(O)H as a special type of Norrish type I reaction.
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