Insights into the mechanistic photodissociation of methyl formate

Journal Article · Thu Jan 21 00:00:00 EST 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3297892· OSTI ID:21559830

Ganglong, Cui; Feng, Zhang; Weihai, Fang ^[1]

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1. Chemistry College, Beijing Normal University, Beijing 100875 (China)

In this work, we studied the photodissociation dynamics of methyl formate (CH{sub 3}OC(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{sub 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{sub 1}) as a result of the S{sub 1}{yields}T{sub 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 CH{sub 3}OC(O)H as a special type of Norrish type I reaction.

• OSTI ID: 21559830
• Journal Information: Journal of Chemical Physics, Vol. 132, Issue 3; Other Information: DOI: 10.1063/1.3297892; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALDEHYDES
CARBONYLS
CHEMICAL BONDS
CLEAVAGE
COMPARATIVE EVALUATIONS
CONFIGURATION INTERACTION
DISSOCIATION
DISSOCIATION ENERGY
EXCITATION
EXCITED STATES
FISSION
FORMATES
KETONES
PHOTOLYSIS
SELF-CONSISTENT FIELD
TRIPLETS
CARBOXYLIC ACID SALTS
CHEMICAL REACTIONS
DECOMPOSITION
ENERGY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EVALUATION
MICROSTRUCTURE
MULTIPLETS
NUCLEAR REACTIONS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS