Effects of vibrational and rotational energies on the lifetime of the pre-reaction complex for the F−+ CH3I SN2 reaction

Ma, Xiaochu; Tan, Xiaojun; Hase, William L.

doi:10.1016/j.ijms.2017.07.011

Cited by 11 publications

(8 citation statements)

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“…In future direct dynamics simulations, it would be of interest to identify the origin of the orbital angular dependence for the product branching ratios and the time-scale for statistical K-mixing. 50 High-level ab initio calculations and additional DFT calculations to investigate the 3 CH 2 + 3 O 2 → CH 2 OO potential energy curves on the singlet and triplet PESs would be useful. UM06/6-311++G(d,p) theory used here gives a barrierless 3 CH 2 + 3 O 2 → CH 2 OO reaction on the singlet PES, consistent with the suggested kinetics, 24 but also a barrierless reaction on the triplet surface.…”

Section: Discussionmentioning

confidence: 99%

“…Branching between the product channels for this statistical excitation may be compared with that for the 3 CH 2 + 3 O 2 → 1 CH 2 OO nonstatistical excitation. In addition to IVR, intramolecular dynamics associated with rotational excitation of 1 CH 2 OO and K-mixing − may also be important. Figure shows that branching between the different product channels on the singlet PES depends on the collision orbital angular momentum, l = μ bv rel .…”

Section: Conclusion and Future Directionsmentioning

confidence: 99%

“…However, at longer times, as a result of vibration–rotation coupling, , a statistical population of the K-levels may occur. In future direct dynamics simulations, it would be of interest to identify the origin of the orbital angular dependence for the product branching ratios and the time-scale for statistical K-mixing …”

Section: Conclusion and Future Directionsmentioning

confidence: 99%

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Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

et al. 2018

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The reaction of CH with O is of fundamental importance in combustion, and the reaction is complex as a result of multiple extremely exothermic product channels. In the present study, direct dynamics simulations were performed to study the reaction on both the singlet and triplet potential energy surfaces (PESs). The simulations were performed at the UM06/6-311++G(d,p) level of theory. Trajectories were calculated at a temperature of 300 K, and all reactive trajectories proceeded through the carbonyl oxide Criegee intermediate, CHOO, on both the singlet and triplet PESs. The triplet surface leads to only one product channel, HCO + O(P), while the singlet surface leads to eight product channels with their relative importance as CO + HO > CO + OH + H ∼ HCO + O(D) > HCO + OH ∼ CO + H ∼ CO + H + O(D) > CO + H + H > HCO + O(D) + H. The reaction on the singlet PES is barrierless, consistent with experiment, and the total rate constant on the singlet surface is (0.93 ± 0.22) × 10 cm molecule s in comparison to the recommended experimental rate constant of 3.3 × 10 cm molecule s. The simulation product yields for the singlet PES are compared with experiment, and the most significant differences are for H, CO, and HO. The reaction on the triplet surface is also barrierless, inconsistent with experiment. A discussion is given of the need for future calculations to address (1) the barrier on the triplet PES for CH + O → CHOO, (2) the temperature dependence of the CH + O reaction rate constant and product branching ratios, and (3) the possible non-RRKM dynamics of the CHOO Criegee intermediate.

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Section: Discussionmentioning

confidence: 99%

Section: Conclusion and Future Directionsmentioning

confidence: 99%

Section: Conclusion and Future Directionsmentioning

confidence: 99%

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Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

et al. 2018

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“…We focus on the F – + CH 3 I system because several theoretical and experimental investigations have been recently performed for this reaction, − providing groundbreaking findings on hydrogen-bonded − ,, and front-side complex formations as well as leaving-group effect . The crossed-beam experiments provided detailed scattering angle and product internal energy distributions, , allowing comparison with theoretical simulations .…”

Section: Introductionmentioning

confidence: 99%

Effects of the Level of Electronic Structure Theory on the Dynamics of the F^– + CH₃I Reaction

et al. 2018

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Accuracy of the different levels of electronic structure theory is frequently studied for stationary-point properties; however, little is known about the effects of the electronic structure methods and basis sets on the dynamics of chemical reactions. Here we report such an investigation for the F + CHI S2 and proton-transfer reactions by developing 20 different analytical potential energy surfaces (PESs) obtained at the HF/DZ, HF/TZ, HF-D3(BJ)/DZ, HF-D3(BJ)/TZ, MP2/DZ, MP2/TZ, MP2-F12/DZ, MP2-F12/TZ, CCSD/DZ, CCSD-F12b/DZ, CCSD(T)/DZ, CCSD(T)-F12b/DZ, OQVCCD(T)/DZ, B97-1/TZ, PBE0/TZ, PBE0-D3(BJ)/TZ, M06-2X/TZ, M06-2X-D3(0)/TZ, B2PLYP/TZ, and B2PLYP-D3(BJ)/TZ levels of theory, where DZ and TZ denote the aug-cc-pVDZ and aug-cc-pVTZ basis sets with a relativistic effective core potential and the corresponding bases for iodine. Millions of quasiclassical trajectories on these PESs reveal that (a) in the case of standard methods, increasing the basis from DZ to TZ decreases the S2 cross sections by 20-30%; (b) the explicitly correlated F12 reactivity is converged with a DZ basis;

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“…Recently, there is growing interest on studying the S N 2 type prereaction complexes by spectral and quantum chemical methods. − However, the question of the structure of intermolecular complexes formed in the first stage of the reaction of N -trimethylsilyl- N -methylacetamide with (chloromethyl)fluorosilanes ClCH 2 SiMe n F 3– n ( n = 0–2) is still unanswered …”

Section: Introductionmentioning

confidence: 99%

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

et al. 2019

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A quantum chemical study has been carried out on the complexes formed in the first stage of the reaction of (chloromethyl)trifluorosilane with an ambident nucleophile, N-trimethylsilyl-N-methylacetamide, existing in the amide and imidate tautomeric forms. The analysis of molecular electrostatic potential maps of the electrophile molecule revealed the presence of two σ-holes belonging to the Si and C atoms. Each of the two tautomers of the nucleophile form complexes having O···Si, O···C, N···Si, and N···C bonds of different characters. The natural bond orbital and quantum theory of atoms in molecules analyses showed the presence of the O···Si and O···C tetrel bonds or of electrostatic interaction in the complexes with the amide tautomer, depending on the orientation of the components. The imidate tautomer forms a complex with covalent N–Si bond, whereas the N···C bond is very weak. The effect of silicon atom arrangement on the structure of complexes between N-trimethylsilyl-N-methylacetamide and bifunctional silanes ClCH2SiX n F3–n (X = Me, OMe, Cl, n = 1, 2) and the effect of σ-hole tetrel bonding interactions on the reaction pathways are discussed.

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Effects of vibrational and rotational energies on the lifetime of the pre-reaction complex for the F−+ CH3I SN2 reaction

Cited by 11 publications

References 53 publications

Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

Effects of the Level of Electronic Structure Theory on the Dynamics of the F^– + CH₃I Reaction

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

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Effects of vibrational and rotational energies on the lifetime of the pre-reaction complex for the F−+ CH3I SN2 reaction

Cited by 11 publications

References 53 publications

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios

Direct Dynamics Simulation of the Thermal 3CH2 + 3O2 Reaction. Rate Constant and Product Branching Ratios

Effects of the Level of Electronic Structure Theory on the Dynamics of the F– + CH3I Reaction

Tetrel Bonding along the Pathways of Transsilylation and Alkylation ofN-Trimethylsilyl-N-methylacetamide with Bifunctional (Chloromethyl)fluorosilanes

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Product

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Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

Direct Dynamics Simulation of the Thermal ³CH₂ + ³O₂ Reaction. Rate Constant and Product Branching Ratios

Effects of the Level of Electronic Structure Theory on the Dynamics of the F^– + CH₃I Reaction