Criegee中间体CH3CHOO与OH自由基反应机理的理论研究

doi:10.7503/cjcu20150742

摘要/Abstract

摘要：

采用CCSD(T)//B3LYP/6-311+G(d,p)方法研究了Criegee中间体CH₃CHOO与OH自由基反应的微观机理. 结果表明, 上述反应存在抽氢、加成-分解和氧化3类反应通道, 其中, syn-CH₃CHOO+OH以抽β-H为优势通道, 表观活化能为-4.88 kJ/mol; anti-CH₃CHOO+OH则以加成-分解反应为优势通道, 表观活化能为-13.25 kJ/mol. 在加成-分解和氧化反应通道中, anti-构象的能垒均低于syn-构象, 而抽氢反应则是syn-(β-H)的能垒低于anti-构象. 速率常数计算表明, anti-构象的加成-分解反应通道具有显著的负温度效应; syn-和anti-构象的氧化通道具有显著的正温度效应. 3类反应具有显著不同的温度效应, 说明通过改变温度可显著调节3类反应的相对速率.

关键词: Criegee中间体, CH3CHOO自由基, OH自由基, 反应机理, 速率常数

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

中图分类号:

O643.1

TrendMD:

高志芳, 王渭娜, 马倩, 刘峰毅, wlwang@snnu.edu.cn. Criegee中间体CH₃CHOO与OH自由基反应机理的理论研究. 高等学校化学学报, 2016, 37(3): 513.

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

图/表 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).

参考文献 30

[1]	Paulson S. E., Chung M. Y., Hasson A. S., J. Phys. Chem. A, 1999, 103(41), 8125—8138
[2]	Jacobson M., Atmospheric Environment, 1997, 31(3), 511—512
[3]	Johnson D., Marston G., Chem. Soc. Rev., 2008, 37(4), 699—716
[4]	Kumar M., Busch D. H., Subramaniam B., Thompson W. H., J. Phys. Chem. A, 2014, 118(10), 1887—1894
[5]	Ryzhkov A. B., Ariya P. A., Phys. Chem. Chem. Phys., 2004, 6(21), 5042—5050
[6]	Qi B., Chao Y. T., Acta Chim. Sinica, 2007, 65(19),2117—2123
	(齐斌, 晁余涛. 化学学报, 2007,65(19), 2117—2123)
[7]	Jiang L., Xu Y.S., Ding A. Z.,J. Phys. Chem. A, 2010, 114(47), 12452—12461
[8]	Bo L., Tan X. F., Long Z. W., Wang Y. B., Ren D. S., Zhang W. J., J. Phys. Chem. A, 2013, 3(8), 1693—1699
[9]	Mansergas A., Anglada J. M., J. Phys. Chem. A, 2006, 110(11), 4001—4011
[10]	Sadezky A., Winterhalter R., Kanawati B., Rompp A., Spengler B., Mellouki A., Bras G. L., Chaimbault P., Moortgat G. K., Atmos. Chem. Phys., 2008, 8(10), 2667—2699
[11]	Kumar M., Busch D. H., Subramaniam B., Thompson W. H., Phys. Chem. Chem. Phys., 2014, 16, 22968—22973
[12]	Nguyen T. N., Putikam R., Lin M. C., J. Chem. Phys., 2015, 142(12), 124312
[13]	Lee S., Kamens R. M., Atmos. Environ., 2005, 39(36), 6822—6832
[14]	Heard D. E., Carpenter L. J., Creasey D. J., Hopkins J. R., Lee J. D., Lewis A. C., Pilling M. J., Seakins P. W., Carslaw N., Emmerson K. M., Geo. Res. Lett., 2004, 31(18), 355—366
[15]	Li H.W., Fang Y., Kidwell N. M., Beames J. M., Lester M. I., J. Phys. Chem. A, 2015, 119(30), 8328—8337
[16]	Kettner M., Karton A., McKinley A. J., Wild D. A., Chemical Physics Letters, 2015, 621, 193—198
[17]	Frisch M.J., T. G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A.G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 09, Gaussian Inc., Wallingford CT, 2009
[18]	Curtiss L. A., Raghavachari K., Redfern P. C., Pople J. A., J. Chem. Phys., 1997, 106, 1063—1079
[19]	Curtiss L. A., Redfern P. C., Raghavachari K., J. Chem. Phys., 2007, 127(12), 66—70
[20]	Zhang S.W., Truong N. T., VKLab Version 1.0, University of Utah,Salt Lake City, 2001
[21]	Kuwata K. T., Hermes M. R., Carlson M. J., Zogg C. K., J. Phys. Chem. A, 2010, 114(34), 9192—9204
[22]	Nakajima M., Yue Q., Endo Y., Journal of Molecular Spectroscopy, 2015, 310, 109—112
[23]	Smith M. C., Ting W. L., Chang C. H., Takahashi K., Boering K. A., Lin J. J. M., J. Chem. Phys., 2014, 141(7), 074302
[24]	Nakajima M., Endo Y., J. Chem. Phys., 2014, 140(1), 011101
[25]	Lin H. Y., Huang Y. H., Wang X., Bowman J. M., Nishimura Y., Witek H. A., Lee Y. P., Nat. Commun., 2015, 6, 7012
[26]	NIST Chemistry Webbook(
[27]	Li D. M., Wang Y., Han K. L., Coord. Chem. Rev., 2012, 256, 1137—1150
[28]	Balucani N., Capozza G., Leonori F., Segoloni E., Casavecchia P., Int. Rev. Phys. Chem., 2006, 25, 109—163
[29]	Guo S., Wang W. N., Jin L. X., Wang S., Wang W. L., Chem. J. Chinese Universities, 2014, 36(8), 1300—1306
	(郭莎, 王渭娜, 靳玲侠, 王帅, 王文亮. 高等学校化学学报, 2014, 36(8), 1300—1306)
[30]	Taatjes C. A., Welz O., Eskola A. J., Savee J. D., Scheer A. M., Shallcross D. E., Rotavera B., Lee E. P. F., Dyke J. M., Mok D. K. W., Osborn D. L., Percival C. J., Science,2013, 340(6129), 177—180

相关文章 15

[1]	周紫璇, 杨海艳, 孙予罕, 高鹏. 二氧化碳加氢制甲醇多相催化剂研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220235.
[2]	杨丹, 刘旭, 戴翼虎, 祝艳, 杨艳辉. 金团簇电催化二氧化碳还原反应的研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220198.
[3]	任娜娜, 薛洁, 王治钒, 姚晓霞, 王繁. 热力学数据对1, 3-丁二烯燃烧特性的影响[J]. 高等学校化学学报, 2022, 43(6): 20220151.
[4]	孙翠红, 吕立强, 刘迎, 王妍, 杨静, 张绍文. 硝酸异丙酯与Cl原子、 OH和NO₃自由基反应的机理及动力学[J]. 高等学校化学学报, 2022, 43(2): 20210591.
[5]	程媛媛, 郗碧莹. ·OH自由基引发CH₃SSC $H 3 •$ ⁺自由基裂解反应机理的理论研究[J]. 高等学校化学学报, 2022, 43(10): 20220271.
[6]	孟繁伟, 高琦, 叶青, 李晨曦. Cu-SAPO-18催化剂氨选择性催化还原NO_x钾中毒机理的研究[J]. 高等学校化学学报, 2021, 42(9): 2832.
[7]	杨一莹, 朱荣秀, 张冬菊, 刘成卜. 金催化炔基苯并二𫫇英环化合成8-羟基异香豆素的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2299.
[8]	李心怡, 刘永军. 人工设计逆醛缩酶RA95.5-8F催化β-羟基酮C—C裂解的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2306.
[9]	李宜蔚, 申屠江涛, 王静波, 李象远. 燃烧反应机理构建的极小反应网络方法： C1燃料燃烧[J]. 高等学校化学学报, 2021, 42(6): 1871.
[10]	田胜侨, 韦美菊. Rh(Ⅱ)催化吲哚衍生物[3+3]环化机理及产物性质分析[J]. 高等学校化学学报, 2021, 42(6): 1899.
[11]	任颖, 李昌华, 王涛, 薛珊珊, 张婷婷, 贾建峰, 武海顺. 钯催化氧化N—H键羰基化反应合成1,3,4⁃噁二唑⁃2(3H)⁃酮杂环化合物机理的理论研究[J]. 高等学校化学学报, 2021, 42(6): 1793.
[12]	齐国栋, 叶晓栋, 徐君, 邓风. 分子筛上糖类催化转化的核磁共振研究[J]. 高等学校化学学报, 2021, 42(1): 148.
[13]	毛庆,赵健,刘松,郭唱,李冰玉,徐可一,曹自强,黄延强. Ni单原子催化剂表面CO₂电还原动力学的电化学谱学解析[J]. 高等学校化学学报, 2020, 41(5): 1058.
[14]	李象远, 申屠江涛, 李宜蔚, 李娟琴, 王静波. 燃烧反应机理构建的极小反应网络方法氢氧燃烧[J]. 高等学校化学学报, 2020, 41(4): 772.
[15]	李象远,姚晓霞,申屠江涛,孙晓慧,李娟琴,刘明夏,许诗敏. 燃烧反应机理构建的双参数速率常数方法[J]. 高等学校化学学报, 2020, 41(3): 512.

Criegee中间体CH₃CHOO与OH自由基反应机理的理论研究

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价