Theoretical Studies on the Reaction Mechanism of Criegee Intermediates CH3CHOO with OH Radicals†

doi:10.7503/cjcu20150742

Abstract

Abstract:

The reaction mechanism of CH₃CHOO with OH was studied at the CCSD(T)//B3LYP/6-311+G(d,p) level. The results show that the detailed mechanism mainly includes hydrogen abstraction, addition-decomposition and oxidation reactions. The calculations show that β-H abstraction reaction is favoured in the syn-CH₃CHOO reaction with OH with a apparent activation energy(E_app) of -4.88 kJ/mol, whereas the addition-decomposition channel is advantaged in the reaction of anti-CH₃CHOO with OH in combination with a E_app of -13.25 kJ/mol. The barriers of anti-CH₃CHOO are lower than that of the syn-CH₃CHOO in addition-decomposition and oxidation reactions, while the syn-CH₃CHOO is lower than anti-CH₃CHOO in the β-H abstraction pathway. The rate constant of addition-decomposition in the reaction of anti-CH₃CHOO satisfies a strong negative temperature dependent, while oxidation channels of syn-/anti-CH₃CHOO obey a positive temperature effect. The temperature dependent of three kind of reactions are different, which makes their relative rate can be controlled by adjusting the temperature.

Key words: Criegee intermediate, CH3CHOO radical, OH radical, Reaction mechanism, Rate constant

CLC Number:

O643.1

TrendMD:

GAO Zhifang, WANG Weina, MA Qian, LIU Fengyi, WANG Wenliang. Theoretical Studies on the Reaction Mechanism of Criegee Intermediates CH₃CHOO with OH Radicals^†[J]. Chem. J. Chinese Universities, 2016, 37(3): 513.

Figures/Tables 8

Scheme 1 Ozonolysis of alkenes forming carbonyl compound and CH3CHOO

Fig.1 Optimized geometries of stationary point of syn-CH3CHOO+OH(A) and anti-CH3CHOO+OH(B) at the B3LYP/6-311+G(d,p) level The values in parentheses are at the CCSD(T)/6-311+G(d,p) level. The bond lengths are in nm.

Table 1 Formation enthalpies ΔfH0— for some species at the G4 level

Species	Δ_fH^0—/(kJ·mol^-1)	Species	Δ_fH^0—/(kJ·mol^-1)
CH₃CHO	-166.54(-170.70^[26])	RC3	91.01
CH₃C(O)OH	-430.54(-432.30^[26])	syn-CH₃CHOO	37.78
CH₂CHOH	-123.67(-128.00^[26])	anti-CH₃CHOO	52.69
CH₃CH(OH)(OO)_PC4	-216.36	syn-CH₂CHOO	108.91
CH₂CH(OH)(OOH)_PC4-2	-142.69	syn-CH₃COO	224.21
CH₃CH(OH)(OO)_PC9	-220.76	anti-CH₂CHOO	104.74
RC1	107.80	anti-CH₃COO	302.44
RC2	84.69

Scheme 2 Possible reaction channels of CH3CHOO with OH radical

Fig.2 Potential energy surface of the hydrogen abstraction at the CCSD(T)// B3LYP/6-311+G(d,p) level

Fig.3 Potential energy surface for addition-decomposition mechanism at the CCSD(T)//B3LYP/6-311+G(d,p) level

Fig.4 Potential energy surface for oxidation mechanism at the CCSD(T)//B3LYP/6-311+G(d,p) level

Fig.5 Fitted plots of the rate constants vs. the reciprocal of temperature for the favorable channels over the range of 200—1000 Ka. syn-β-Hab(R2); b. syn-Oxi(R3); c. syn-Add(R5); d. anti-α-Hab(R6); e. anti-Oxi(R8); f. anti-Add(R10).

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Theoretical Studies on the Reaction Mechanism of Criegee Intermediates CH₃CHOO with OH Radicals^†

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