Variational transition state theory rate constants and H/D kinetic isotope effects for CH3 + CH3OCOH reactions |
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Authors: | Edson F V de Carvalho Guilherme D Vicentini Tiago Vinicius Alves Orlando Roberto-Neto |
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Institution: | 1. Departamento de Física, Universidade Federal do Maranhão, São Luís, 65085-580 Maranhão, Brazil;2. Divisão de Aerotermodinâmica e Hipersônica, Instituto de Estudos Avançados, São José dos Campos, 12228-001 São Paulo, Brazil;3. Departamento de Físico-Química, Instituto Química, Universidade Federal da Bahia, Salvador, 40170-115 Bahia, Brazil |
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Abstract: | The rate constants and H/D kinetic isotope effect for hydrogen abstraction reactions involving isotopomers of methyl formate by methyl radical are computed employing methods of the variational transition state theory (VTST) with multidimensional tunneling corrections. The energy paths were built with a dual-level method using the moller plesset second-order perturbation theory (MP2) method as the low-level and complete basis set (CBS) extrapolation as the high-level energy method. Benchmark calculations with the CBSD-T approach give an enthalpy of reaction at 0 K for R1 (−4.5 kcal/mol) and R2 (−4.2 kcal/mol) which are in good agreement with the experiment, that is, −4.0 and − 4.8 kcal/mol. For the reactional paths involving the isotopomers CH3 + CH3OCOH → CH4 + CH3OCO and CH3 + CH3OCOD → CH3D + CH3OCO, the value of kH/kD (T = 455 K) using the canonical VTST/small-curvature tunneling approximation method is 6.7 in close agreement with experimental value (6.2). © 2019 Wiley Periodicals, Inc. |
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Keywords: | methyl formate methyl abstractor CBS variational transition state theory rate constants kinetic isotope effect |
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