Rotationally resolved infrared spectrum of the Br––D2 anion complex
The midinfrared spectrum of the 79Br––D2 anion complex is measured in the D2 stretch region by monitoring the production of Br– photofragments in a tandem mass spectrometer. The rotatio...
The midinfrared spectrum of the 79Br––D2 anion complex is measured in the D2 stretch region by monitoring the production of Br– photofragments in a tandem mass spectrometer. The rotatio...
Hydrogen bonding and collective proton modes in clusters and periodic layers of squaric acid: A density functional study
Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energ...
Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energ...
Ring closure in dioxin formation process: An ab initio molecular dynamics study
J. Chem. Phys. 115, 6401 (2001); doi:10.1063/1.1402164
Issue Date: 8 October 2001
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The four possible mechanisms of ring closure in dioxin formation from chlorophenols are studied using ab initio molecular dynamics, within generalized gradient approximation. Free energy barriers, derived as the potential of mean constraint force, directly lead to a static approximation for the transition rates. We show, however, that the static approximation overestimates the actual rates by 33%–345%, depending on the intermediate/temperature. Comparing our results with the available experimental data, we conclude that, contrary to what is widely assumed, the pathways starting from two chlorophenols are not among the most dominant pathways in the formation of highly toxic dioxins, at least in the gas phase. This signifies the role of catalysts and/or other precursors. ©2001 American Institute of Physics.
| History: | Received 17 April 2001; accepted 20 July 2001 |
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BibSonomy
KEYWORDS and PACS
organic compounds,
chemical reactions,
ab initio calculations,
molecular dynamics method,
free energy,
density functional theory,
reaction kinetics theory
- 82.30.-b
Physical chemistry and chemical physics Specific chemical reactions; reaction mechanisms - 82.20.Pm
Physical chemistry and chemical physics Chemical kinetics and dynamics Rate constants, reaction cross sections, and activation energies - 82.20.Db
Physical chemistry and chemical physics Chemical kinetics and dynamics Transition state theory and statistical theories of rate constants - 82.20.Hf
Physical chemistry and chemical physics Chemical kinetics and dynamics Product distribution - YEAR: 2001
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0021-9606 (print)
1089-7690 (online)
AIP
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