Ab initio and RRKM calculations for the decomposition channels of CH3OBr and BrCH2OH

Papayannis, Demetrios K.; Drougas, Evangelos; Kosmas, Agnie M.

doi:10.1016/s0301-0104(02)00720-6

Cited by 12 publications

(13 citation statements)

References 42 publications

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“…The energetically most favorable reaction path is CH 3 CH 2 OBr → CH 3 CH 2 O + Br which is consistent with the main decomposition channel of CH 3 OBr being OBr bond scission19. This is a single OBr bond fission process without a well‐defined transition state.…”

Section: Resultssupporting

confidence: 73%

“…Based on aforementioned analysis, the main products of the O( 1 D) + CH 3 CH 2 Br reaction are probably the main products of IM1, CH 3 COH + HBr and CH 2 CHOH + HBr. As there are no direct experimental or theoretical results that we can compare to, we compare our results to the decompositions of O( 3 P) + CH 3 CH 2 Br18 and BrCH 2 OH, CH 3 OBr19. In Ref.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, Wang et al18, have studied the potential energy surface of the reaction O( 3 P) + CH 3 CH 2 Br; according to their study, the reaction reveals an indirect abstraction mechanism. Quantum mechanical and RRKM calculations are carried out to study the potential energy surface and the kinetics for the decomposition channels of CH 3 OBr and BrCH 2 OH19. The OBr bond scission to CH 3 O + Br products are the main products of the decomposition of CH 3 OBr and HBr elimination channel is the main decomposition channel of BrCH 2 OH.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Tian

Song

2010

Int J of Quantum Chemistry

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The potential energy surface of O( 1 D) þ CH 3 CH 2 Br reaction has been studied using QCISD(T)/6-311þþG(d,p)//MP2/6-311G(d,p) method. The calculations reveal an insertion-elimination reaction mechanism of the title reaction. The insertion process has two possibilities: one is the O( 1 D) inserting into CABr bond of CH 3 CH 2 Br producing one energy-rich intermediate CH 3 CH 2 OBr and another is the O( 1 D) inserting into one of the CAH bonds of CH 3 CH 2 Br producing two energy-rich intermediates, IM1 and IM2. The three intermediates subsequently decompose to various products. The calculations of the branching ratios of various products formed though the three intermediates have been carried out using RRKM theory at the collision energies of 0, 5, 10, 15, 20, 25, and 30 kcal/mol. CH 3 CH 2 O þ Br are the main decomposition products of CH 3 CH 2 OBr. CH 3 COH þ HBr and CH 2 CHOH þ HBr are the main decomposition products for IM1; CH 2 CHOH þ HBr are the main decomposition products for IM2. As IM1 is more stable and more likely to form than CH 3 CH 2 OBr and IM2, CH 3 COH þ HBr and CH 2 CHOH þ HBr are probably the main products of the O( 1 D) þ CH 3 CH 2 Br reaction. Our computational results can give insight into reaction mechanism and provide probable explanations for future experiments.

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Tian

Song

2010

Int J of Quantum Chemistry

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“…CH 3 CH 2 O + F which is in consistent with the main decomposition channel of CH 3 OBr being O-Br bond scission [31]. This is a single O-F bond fission process without a well-defined transition state.…”

Section: Decomposition Of Ch 3 Ch 2 Ofsupporting

confidence: 79%

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(1D) with CH3CH2F

Song

Tian

et al. 2009

Journal of Molecular Structure: THEOCHEM

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“…The k(E i , J ) was computed with the Beyer-Swinehart algorithm 60 to determine the number of states implemented in the SuperRRKM program. [62][63][64][65][66] The calculated values of E* as well as the geometries, energies and vibrational frequencies are available in the ESI. These thermal contributions were calculated at 298 K and rotational effects were not considered ( J = 0).…”

Section: Rrkm Calculationsmentioning

confidence: 99%

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

Proenza

Souza

Ventura

et al. 2014

Phys. Chem. Chem. Phys.

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The energetics of the E CO 2, S N 2@C and S N 2@N channels of X À + CH 3 ONO 2 (X = F, OH, CH 2 CN) gas-phase reactions were computed using the CCSD(T)/CBS method. This benchmark extends a previous study with X = OH [M. A. F. de Souza et al., J. Am. Chem. Soc., 2012, 134, 19004] and was used to ascertain the accuracy and robustness of nineteen density-functionals for describing these potential energy profiles (PEP) as well as the kinetic product distributions obtained from RRKM calculations. Assessments were based on the mean unsigned error (MUE), the mean signed error (MSE), the #best : #worst (BW) criterion and the statistical confidence interval (CI) for the MSE. In general, double-hybrid (DH) functionals perform better than the range-separated ones, and both are better than the global-hybrid functionals. Based on the MUE and CI criteria the B2GPPLYP, B2PLYP, M08-SO, BMK, oB97X-D, CAM-B3LYP, M06, M08-HX, oB97X and B97-K functionals show the best performance in the description of these PEPs. Within this set, the B2GPPLYP functional is the most accurate and robust. The RRKM results indicate that the DHs are the best for describing the selectivities of these reactions. Compared to CCSD(T), the B2PLYP method has a relative error of only ca. 1% for the selectivity and the accuracy to provide the correct conclusion concerning the nonstatistical behavior of these reactions.Scheme 1 Reaction channels for the X À + CH 3 ONO 2 (X = F, 18 OH, CH 2 CN) systems with their experimental relative product distributions 28,30 and experimental DH 0 values 31 (in kcal mol À1 ).

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Ab initio and RRKM calculations for the decomposition channels of CH3OBr and BrCH2OH

Cited by 12 publications

References 42 publications

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(1D) with CH3CH2F

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN

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Ab initio and RRKM calculations for the decomposition channels of CH3OBr and BrCH2OH

Cited by 12 publications

References 42 publications

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(1D) with CH3CH2Br

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(1D) with CH3CH2Br

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(1D) with CH3CH2F

Assessment of density-functionals for describing the X−+ CH3ONO2gas-phase reactions with X = F, OH, CH2CN

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Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Ab initio study of the potential energy surface and product branching ratios for the reaction of O(¹D) with CH₃CH₂Br

Assessment of density-functionals for describing the X⁻+ CH₃ONO₂gas-phase reactions with X = F, OH, CH₂CN