Transition state geometry in radical abstraction reactions: comparison of interatomic distances in the intersecting parabolas and Morse curves models with quantum-chemical calculations |
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Authors: | Shestakov A. F. Denisov E. T. |
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Affiliation: | (1) Institute of Problems of Chemical Physics, Russian Academy of Sciences, 14 Institutskii prosp., 142432 Chernogolovka, Moscow Region, Russian Federation |
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Abstract: | Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H· + H2, H· + HCl, H· + CH4, N·H2 + NH3, HO· + H2O, HO2· + HOOH, and C·H3 + SiH4. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10–12 m for IPM and a = +1.9·10–12 m for IMM. |
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Keywords: | quantum chemistry interatomic distance density functional method intersecting parabolas method intersecting Morse curves method free radical abstraction reaction transition state geometry |
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