Quantum Mechanical Approach to Leucine + OH Gas Phase Reaction. Mechanism and Kinetics
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| Format: | Artículo científico |
| Language: | en |
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Sociedad Química de México
2004
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| _version_ | 1876489585442160640 |
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| author | Annia Galano |
| author_facet | Annia Galano |
| contents | Quantum Mechanical Approach to Leucine + OH Gas Phase Reaction. Mechanism and Kinetics Annia Galano J. Raúl Álvarez Idaboy Esther Agacino Ma. Esther Ruiz Santoyo Multidisciplinaria (Ciencias Naturales y Exactas) rate leucine mechanism OH radical H abstraction The gas phase OH hydrogen abstraction reaction fromleucine has been studied using Density Functional Theory (B3LYP)calculations and the 6-311G(d,p) basis set. The structures of the differentstationary points are discussed. Reaction profiles are modeledincluding the formation of pre-reactive complexes, and negative netactivation energy is obtained for the overall reaction. BSSE correctionsare included. A complex mechanism is proposed, and the ratecoefficients are calculated using Transition State Theory over thetemperature range 250 350 K. The rate coefficients are proposed forthe first time and it was found that in the gas phase the hydrogenabstraction occurs almost exclusively from the gamma site. The followingexpressions, in L⋅mol-1⋅s-1, are obtained for the alpha andgamma H-abstraction channels, and for the overall temperaturedependent rate constants, respectively: kα = (2.19 ± 0.05) x 107exp[(905 ± 12)/T], kγ = (3.19 ± 0.05) x 107 exp[(2450 ± 10)/T], andktot = (3.80 ± 0.08) x 107 exp[(2378 ± 12)/T]. 2004 artículo científico 1870-249X https://www.redalyc.org/articulo.oa?id=47548206 en http://www.redalyc.org/revista.oa?id=475 Journal of the Mexican Chemical Society application/pdf Sociedad Química de México Journal of the Mexican Chemical Society (México) Num.2 Vol.48 |
| format | Artículo científico |
| id | redalyc_47548206 |
| institution | Redalyc |
| language | en |
| publishDate | 2004 |
| publisher | Sociedad Química de México |
| spellingShingle | Quantum Mechanical Approach to Leucine + OH Gas Phase Reaction. Mechanism and Kinetics Annia Galano Multidisciplinaria (Ciencias Naturales y Exactas) rate leucine mechanism OH radical H abstraction Quantum Mechanical Approach to Leucine + OH Gas Phase Reaction. Mechanism and Kinetics Annia Galano J. Raúl Álvarez Idaboy Esther Agacino Ma. Esther Ruiz Santoyo Multidisciplinaria (Ciencias Naturales y Exactas) rate leucine mechanism OH radical H abstraction The gas phase OH hydrogen abstraction reaction fromleucine has been studied using Density Functional Theory (B3LYP)calculations and the 6-311G(d,p) basis set. The structures of the differentstationary points are discussed. Reaction profiles are modeledincluding the formation of pre-reactive complexes, and negative netactivation energy is obtained for the overall reaction. BSSE correctionsare included. A complex mechanism is proposed, and the ratecoefficients are calculated using Transition State Theory over thetemperature range 250 350 K. The rate coefficients are proposed forthe first time and it was found that in the gas phase the hydrogenabstraction occurs almost exclusively from the gamma site. The followingexpressions, in L⋅mol-1⋅s-1, are obtained for the alpha andgamma H-abstraction channels, and for the overall temperaturedependent rate constants, respectively: kα = (2.19 ± 0.05) x 107exp[(905 ± 12)/T], kγ = (3.19 ± 0.05) x 107 exp[(2450 ± 10)/T], andktot = (3.80 ± 0.08) x 107 exp[(2378 ± 12)/T]. 2004 artículo científico 1870-249X https://www.redalyc.org/articulo.oa?id=47548206 en http://www.redalyc.org/revista.oa?id=475 Journal of the Mexican Chemical Society application/pdf Sociedad Química de México Journal of the Mexican Chemical Society (México) Num.2 Vol.48 |
| title | Quantum Mechanical Approach to Leucine + OH Gas Phase Reaction. Mechanism and Kinetics |
| topic | Multidisciplinaria (Ciencias Naturales y Exactas) rate leucine mechanism OH radical H abstraction |
| url | https://www.redalyc.org/articulo.oa?id=47548206 |