CF2ClC(O)OCH2CH3+OH的反应机理及动力学性质的理论研究

doi:10.7503/cjcu20150568

摘要/Abstract

摘要：

利用双水平直接动力学方法, 在MCG3-MPWB//M06-2X/aug-cc-pVDZ水平上研究了CF₂ClC(O)OCH₂CH₃+OH的微观反应机理. 得到了反应物CF₂ClC(O)OCH₂CH₃的5种稳定构象(RC1~RC5), 并对每一构象考察了发生在—CH₃和—CH₂—基团上的所有可能氢提取反应通道. 利用改进的变分过渡态理论(ICVT)结合小曲率隧道效应校正(SCT)计算了各反应通道的速率常数, 分析了各构象反应位点选择性. 结果表明, 对于构象RC1和RC2, 低温时氢提取反应主要发生在—CH₂—基团上; 而对于构象RC3, RC4和RC5, 发生在—CH₃基团上的氢提取反应通道在整个温度区间内占绝对优势. 根据Boltzmann配分函数计算总包反应速率常数, 在298 K温度下计算的体系总包反应速率常数与实验值相符, 进而给出200~1000 K温度范围内拟合了速率常数的三参数Arrhenius表达式: k_overall=5.45×10^-25 T^4.54 exp(-685/T).

关键词: 直接动力学方法, 速率常数, 变分过渡态理论, 密度泛函理论, 反应机理

Abstract:

The mechanism of the hydrogen abstraction reaction of CF₂Cl(O)OCH₂CH₃+OH was studied theoretically via a dual-level direct dynamics method at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level. Five stable conformers(RC1—RC5) of the reactant CF₂Cl(O)OCH₂CH₃ were located, and for each conformer, the possible H-abstraction channels from —CH₃ and —CH₂— groups were taken into account. The rate constants were calculated using the improved canonical variational transition-state theory(ICVT) with the small-curvature tunneling correction(SCT) and the selectivity of the reaction sites of CF₂Cl(O)OCH₂CH₃ was evaluated. The results show that for the conformers RC1 and RC2, the H-abstraction reactions mainly take place at the —CH₂— group at low temperature, while for the conformers RC3, RC4 and RC5, the hydrogen abstraction from the —CH₃group is the major channel in the whole considered temperature range. The overall rate constant is obtained by considering the weight factors of the five conformers calculated from the Boltzmannn distribution function. It is found, that the calculated k_overall at 298 K is in good agreement with the available experimental data. The three parameter expression for the overall reaction within 200—1000 K is fitted to k_overall=5.45×10^-25 T^4.54 exp(-685/T).

Key words: Direct dynamics method, Rate constant, Variational transition-state theory, Density functional theory, Reaction mechanism

中图分类号:

O641
O643

TrendMD:

朱鹏, 段雪梅, 刘靖尧. CF₂ClC(O)OCH₂CH₃+OH的反应机理及动力学性质的理论研究. 高等学校化学学报, 2016, 37(1): 79.

ZHU Peng, DUAN Xuemei, LIU Jingyao. Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF₂ClC(O)OCH₂CH₃ with OH Radicals^†. Chem. J. Chinese Universities, 2016, 37(1): 79.

图/表 9

Fig.1 Optimized geometries parameters of conformers RC1—RC5 at the M06-2X/aug-cc-pVDZ level^Bond lengths are in nm and bond angles are in degree.

Fig.2 Torsional potential profiles for torsion angle Cl—C—C—O for RC1(A), torsion angle C—O—C—C for RC1(B) and torsion angle Cl—C—C—O for RC3(C)

Fig.3 Optimized geometry parameters of reactants, products, transition-states, and hydrogen-bond complexes for the H-abstraction channels of R4 at the M06-2X/aug-cc-Pvdz^Bond lengths are in nm and angles are in degree.

Table 1 Standard enthalpies of formation() at 298 K calculated at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level

Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)	Species	/ (kJ·mol^-1)
RC1	-838.47	RC2	-843.49	RC3	-837.22	RC4	-843.08	RC5	-842.24
P1a	-625.09	P2a	-630.53	P3a	-626.76	P4a	-631.78	P5a	-631.37
P1b	-628.02	P2b	-633.04	P3b	-649.78	P4b	-640.99	P5b	-654.38
P1c	-649.78	P2c	-654.13	P3c	-636.80	P4c	-653.54	P5c	-640.99

Fig.4 Schematic potential energy profiles for the RC1+OH reaction(A), the RC2+OH reaction(B), the RC3+OH reaction(C), the RC4+OH reaction(D) and the RC5 + OH reaction(E)^Relative energies with ZPE atthe MCG3-MPWB//M06-2X/aug-cc-pVDZ level are in kJ/mol.

Fig.5 TST, ICVT and ICVT/SCT rate constants calculated at the MCG3-MPWB//M06-2X/aug-cc-pVDZ level versus 1000/T between 200 and 1000 K for path (R4c)(A) and for path (R4e)(B)

Fig.6 Plots of the calculated branching ratios versus 1000/T between 200 and 1000 K for the reaction RC1+OH→products(A) and the reaction RC4+OH→products(B)

Table 2 Rate constants for each conformer and the overall rate constant[koverall/(cm3·molecule-1·s-1)] in the temperature range 200—1000 K at the MCG3-MPWB//M06-2X level

T/K	10¹² k₁	10¹² k₂	10¹² k₃	10¹² k₄	10¹² k₅	10¹² k_overall
200	0.355	0.464	0.471	0.551	0.360	0.464
250	0.425	0.756	0.614	0.695	0.516	0.645
296	0.529	1.12	0.803	0.877	0.796	0.898
298	0.536	1.14	0.813	0.888	0.812	0.912(0.54±0.15)^[3]
350	0.705	1.67	1.11	0.161	1.40	1.34
400	0.926	2.31	1.50	0.149	2.35	1.92
500	1.56	4.06	2.64	0.236	6.12	3.80
600	2.53	6.51	4.40	3.60	13.7	7.03
800	5.88	14.1	10.4	7.33	47.5	19.4
1000	11.8	26.1	20.7	13.2	121	43.5

Fig.7 Plot of the contributions of RC1, RC2, RC3, RC3 and RC4 to the reaction versus 1000/T between 200 and 1000 K

参考文献 32

[1]	Oyaro N., Sellevag S. R., Nielsen C. J., Environ. Sci. Technol., 2004, 38, 5567—5576
[2]	Sulback Andersen M. P., Nielsen O. J., Wallington T. J., Hurley M. D., DeMoore G. W., J. Phys. Chem. A, 2005, 109, 3926—3934
[3]	Blanco M. B., Teruel M. A., Chem. Phys. Lett., 2007, 441, 1—6
[4]	Hu W. P., Truhlar D. G., J. Am. Chem. Soc., 1996, 118, 860—869
[5]	Truhlar D. G., Garrett B. C., Klippenstein S. J., J. Phys. Chem., 1996, 100, 12771—12800
[6]	Truhlar D. G., Gordon M. S., Science,1990, 249, 491—498
[7]	Tucker S.C., Truhlar D. G., New Theoretical Concepts for Understanding Organic Reaction, Kluwer,Dordrecht, 1989, 291—346
[8]	Truhlar D. G., Gordon M. S., Stechler R., Chem. Rev., 1987, 87, 217—236
[9]	Lu D. H., Truong T. N., Melissas V. S., Lynch G. C., Liu Y. P., Grarrett B. C., Stechler R., Issacson A. D., Rai S. N., Hancock G. C., Lauderdale J. G., Joseph T., Truhlar D. G., Comput. Phys. Commum., 1992, 71, 235—262
[10]	Garrett B. C., Truhlar D. G., J. Phys. Chem., 1991, 95, 10374—10379
[11]	Truhlar D. G., Garrett B. C., Acc. Chem. Res., 1980, 13, 440—448
[12]	Truhlar D. G., Garrett B. C., Annu. Rev. Phys. Chem., 1984, 35, 159—189
[13]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A.F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam N. J., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.1, Gaussian Inc.,Wallingford CT, 2009
[14]	Zhao Y., Truhlar D.G., Theor. Chem. Acc., 2008, 120, 215—241
[15]	Zhao Y., Truhlar D. G., J. Phys. Chem. A, 2005, 109, 4209—4212
[16]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Zakrzewski V. G., Montgomery J. A. Jr., Stratmann R. E., Burant J. C., Dapprich S., Millam J. M., Daniels A. D., Kudin K. N., Strain M. C., Farkas O., Tomasi J., Barone V., Cossi M., Cammi R., Mennucci B., Pomelli C., Adamo C., Clifford S., Ochterski J., Petersson G. A., Ayala P. Y., Cui Q., Morokuma K., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Cioslowski J., Ortiz J. V., Boboul A. G., Stefnov B. B., Liu G., Liaschenko A., Piskorz P., Komaromi L., Gomperts R., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Gonzalez C., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Andres J. L., Gonzalez C., Head-Gordon M., Replogle E. S., Pople J. A, Gaussian 03, Revision A.1, Guassian Inc.,Pittsburgh PA, 2003
[17]	Zhao Y., Truhlar D.G., MLGAUSS-Version 2.0, University of Minnesota, Minneapolis, 2005
[18]	Chuang Y. Y., Corchado J. C., Truhlar D. G., J. Phys. Chem. A, 1999, 103, 1140—1149
[19]	Garrett B. C., Truhlar D. G., Grev R. S., Magnuson A. W., J. Phys. Chem., 1980, 84, 1730—1748
[20]	Truhlar D. G., J. Comput. Chem., 1991, 12, 266—270
[21]	Liu Y. P., Lynch G. C., Truong T. N., Lu D. H., Truhlar D. G., Garrett B. C., J. Am. Chem. Soc., 1993, 115, 2408—2415
[22]	Galano A., Alvarez-Idaboy J. R., Ruiz-Santoyo M. E., Vivier-Bunge A., Chem.Phys.Chem,2004, 5, 1379—1388
[23]	Taghikhani M., Parsafar G. A., Sabzyan H., J. Phys. Chem. A, 2005, 109, 8158—8167
[24]	Wang Y. X., Gao H., Wang Q., Liu J. Y., Chem. J. Chinese Universities, 2010, 31(6), 1240—1245
	(王永霞, 高红, 王钦, 刘靖尧. 高等学校化学学报, 2010, 31(6), 1240—1245)
[25]	Ren H., Zhang L. L., Wang R. S., Pan X. M., J. Phys. Chem. A, 2012, 116, 10647—10655
[26]	Jin T. Y., Wang Q., Liu J. Y., Chem. J. Chinese Universities, 2013, 34(3), 641—649
	(金铜音, 王钦, 刘靖尧. 高等学校化学学报, 2013, 34(3), 641—649)
[27]	Zhu P., Ai L. L., Wang H., Liu J. Y., Comput. Theor. Chem., 2014, 1029, 91—98
[28]	Zhu P., Duan X. M., Liu J. Y., J. Fluorine. Chem., 2015, 176, 61—70
[29]	Corchado J.C., Chuang Y. Y., Fast P. L., Hu W. P., Liu Y. P., Lynch G. C., Nguyen K. A., Jackels C. F., Ramos A. F., Ellingson B. A., Lynch B. J., Melissas V. S., Villa J., Rossi I., Coitino E. L., Pu J., Albu T. V., Steckler R., Garrett B. C., Isaacson A. D., Truhlar D. G., POLYRATE, Version 9.7, University of Minnesota,Minneapolis, 2007
[30]	Jin X. H., Hu B. C., Jia H. Q., Lu C. X., Chem. J. Chinese Universities, 2013, 34(7), 1685—1690
	(金兴辉, 胡炳成, 贾欢庆, 吕春绪. 高等学校化学学报, 2013, 34(7), 1685)
[31]	Wang H. X., Wang B. Y., Zhang J. L., Li Z. R., Li X. Y., Chem. J. Chinese Universities, 2011, 32(5), 1123—1128
	(王海霞, 汪必耀, 张俊玲, 李泽荣, 李象远. 高等学校化学学报, 2011, 32(5), 1123—1128)
[32]	Linstrom P.JMallard W. G.NIST Chemistry Webbook,

相关文章 15

[1]	何鸿锐, 夏文生, 张庆红, 万惠霖. 羟基氧化铟团簇与二氧化碳和甲烷作用的密度泛函理论研究[J]. 高等学校化学学报, 2022, 43(8): 20220196.
[2]	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.
[3]	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.
[4]	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.
[5]	黄汉浩, 卢湫阳, 孙明子, 黄勃龙. 石墨炔原子催化剂的崭新道路:基于自验证机器学习方法的筛选策略[J]. 高等学校化学学报, 2022, 43(5): 20220042.
[6]	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.
[7]	刘洋, 李旺昌, 张竹霞, 王芳, 杨文静, 郭臻, 崔鹏. Sc₃C₂@C₈₀与[12]CPP纳米环之间非共价相互作用的理论研究[J]. 高等学校化学学报, 2022, 43(11): 20220457.
[8]	王园月, 安梭梭, 郑旭明, 赵彦英. 5-巯基-1, 3, 4-噻二唑-2-硫酮微溶剂团簇的光谱和理论计算研究[J]. 高等学校化学学报, 2022, 43(10): 20220354.
[9]	周成思, 赵远进, 韩美晨, 杨霞, 刘晨光, 贺爱华. 硅烷类外给电子体对丙烯-丁烯序贯聚合的调控作用[J]. 高等学校化学学报, 2022, 43(10): 20220290.
[10]	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.
[11]	钟声广, 夏文生, 张庆红, 万惠霖. 电中性团簇MCu₂O_x(M=Cu²⁺, Ce⁴⁺, Zr⁴⁺)上甲烷和二氧化碳直接合成乙酸的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2878.
[12]	马丽娟, 高升启, 荣祎斐, 贾建峰, 武海顺. Sc, Ti, V修饰B/N掺杂单缺陷石墨烯的储氢研究[J]. 高等学校化学学报, 2021, 42(9): 2842.
[13]	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.
[14]	黄罗仪, 翁约约, 黄旭慧, 王朝杰. 车前草中黄酮类成分结构和性质的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2752.
[15]	王建, 张红星. 四配位铂磷光发射体结构与光物理性质关系的理论研究[J]. 高等学校化学学报, 2021, 42(7): 2245.

CF₂ClC(O)OCH₂CH₃+OH的反应机理及动力学性质的理论研究

Mechanism and Kinetics of the Hydrogen-abstraction Reaction of CF₂ClC(O)OCH₂CH₃ with OH Radicals^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价