Quantum scattering study of the abstraction reactions of H atoms from CH3NH2

Kerkeni, Boutheı̈na; Clary, David C.

doi:10.1016/j.cplett.2007.02.046

Cited by 31 publications

(39 citation statements)

References 27 publications

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“…In order to reduce the complexity in calculating the centre of mass of the reactants, we assumed that the COM of the TMS is situated on the carbon atom from which the H atom is abstracted, thereby neglecting the COM correction. This approximation, introduced in the studies of H atom abstraction reactions from CH 3 OH, C 2 H 6 , C 3 H 8 [18,23], CH 3 NH 2 [20] and n-C 4 H 10 [24], led to rate constants in good agreement with the experimental data. Therefore R 1 and R 2 are defined respectively as (r 1 +r 2 /2) and as r 2 [18], where r 1 and r 2 are respectively the interatomic distances of the breaking and the forming bonds (Cf.…”

Section: Ab Initio Calculationssupporting

confidence: 64%

“…Over the past years, this approach was developed in 2D-and 3D-dimensions and was successfully employed to study the Habstraction reaction from small molecules like C1-C3 alkanes and methanol [17][18][19][20][21][22][23] and recently to n-butane [24] and to spin-orbit non adiabatic transitions [25]. Quantum tunneling is found to be important and the calculated thermal rates agree well with the experiments.…”

Section: Introductionsupporting

confidence: 60%

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Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Oueslati

Kerkeni

Tchang-Brillet

et al. 2015

Chemical Physics Letters

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Section: Ab Initio Calculationssupporting

confidence: 64%

Section: Introductionsupporting

confidence: 60%

Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Oueslati

Kerkeni

Tchang-Brillet

et al. 2015

Chemical Physics Letters

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“…Zhang et al [17] had investigated the reaction of CH 3 NH 2 with H at the QCISD(T)/6-311ϩG(3df,2p)//MP2/6-311G(2d,2p) level of theory in conjunction with rate constant prediction by the canonical variational transition state theory with small-curvature tunneling correction over a wide temperature range of 200 to 3000. Kerkeni and Clary [18] studied the same reaction by the reduced dimensionality quantum dynamical calculations of the rate constants and the branching ratios.…”

Section: Introductionmentioning

confidence: 98%

Direct dynamics study on the mechanism and the kinetics of the reaction of CH₃NH₂ with OH

Tian

Wang

Zhang

et al. 2009

Int J of Quantum Chemistry

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ABSTRACT:A theoretical study of the mechanism and the kinetics for the hydrogen abstraction reaction of methylamine by OH radical has been presented at the CCSD(T)/ 6-311 ϩϩG(2d,2p)//CCSD/6-31G(d) level of theory. Our theoretical calculations suggest a stepwise mechanism involving the formation of a prereactant complex in the entrance channel and a preproduct complex in the exit channel, for the two hydrogen abstraction channels involving the methyl and amine groups. For clarity, the diagram of potential for the reaction is given. The calculated standard reaction enthalpies are Ϫ98.48 and Ϫ76.50 kJ mol Ϫ1 and barrier heights are 0.36 and 25.25 kJ mol Ϫ1, respectively. The rate constants are evaluated by means of the improved canonical variational transition state theory with small-curvature tunneling correction (ICVT/SCT) in the temperature range of 299 -3000 K. The calculated results show that the rate constants at experimentally measured temperatures are in good agreement with the experimental values. It is shown that the calculated rate constants exhibit a non-Arrhenius behavior. Moreover, the variational effect is obvious in the calculated temperature range. The dominant product channel is to form CH 2 NH 2 and H 2 O via hydrogen abstraction from the CH 3 group of CH 3 NH 2 by OH in the calculated temperature range.

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“…49 Internal degrees of freedom (DOF) are divided into two active modes explicitly treated in the quantum scattering, and 3N −8 spectator modes, which are approximately treated via inclusion of curvilinear-projected zero-point energies (ZPE) in the PES. 50,51 Variants of this approach have been successfully applied to a number of ground state reactions, 49,[52][53][54][55][56] including Cl + CH 4 − → HCl + CH 3 . 11 In this paper, the method is extended to include multisurface characterization of nonadiabatic transitions.…”

mentioning

confidence: 99%

Reduced dimensionality spin-orbit dynamics of CH3 + HCl $\rightleftharpoons$⇌ CH4 + Cl on ab initio surfaces

Remmert

Banks

Harvey

et al. 2011

The Journal of Chemical Physics

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A reduced dimensionality quantum scattering method is extended to the study of spin-orbit nonadiabatic transitions in the CH 3 + HCl − − CH 4 + Cl( 2 P J ) reaction. Three two-dimensional potential energy surfaces are developed by fitting a 29 parameter double-Morse function to CCSD(T)/IB//MP2/cc-pV(T+d)Z-dk ab initio data; interaction between surfaces is described by geometry-dependent spin-orbit coupling functions fit to MCSCF/cc-pV(T+d)Z-dk ab initio data. Spectator modes are treated adiabatically via inclusion of curvilinear projected frequencies. The total scattering wavefunction is expanded in a vibronic basis set and close-coupled equations are solved via R-matrix propagation. Ground state thermal rate constants for forward and reverse reactions agree well with experiment. Multi-surface reaction probabilities, integral cross sections, and initial-state selected branching ratios all highlight the importance of vibrational energy in mediating nonadiabatic transition. Electronically excited state dynamics are seen to play a small but significant role as consistent with experimental conclusions.

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Quantum scattering study of the abstraction reactions of H atoms from CH3NH2

Cited by 31 publications

References 27 publications

Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Direct dynamics study on the mechanism and the kinetics of the reaction of CH₃NH₂ with OH

Reduced dimensionality spin-orbit dynamics of CH3 + HCl $\rightleftharpoons$⇌ CH4 + Cl on ab initio surfaces

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Quantum scattering study of the abstraction reactions of H atoms from CH3NH2

Cited by 31 publications

References 27 publications

Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Quantum scattering study of the abstraction reaction of H atoms from tetramethylsilane

Direct dynamics study on the mechanism and the kinetics of the reaction of CH3NH2 with OH

Reduced dimensionality spin-orbit dynamics of CH3 + HCl $\rightleftharpoons$⇌ CH4 + Cl on ab initio surfaces

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Direct dynamics study on the mechanism and the kinetics of the reaction of CH₃NH₂ with OH