烷基自由基β位裂解反应类反应势垒与速率常数的精确计算

doi:10.3866/PKU.WHXB201209053

物理化学学报 >> 2012, Vol. 28 >> Issue (12): 2824-2830.doi: 10.3866/PKU.WHXB201209053

烷基自由基β位裂解反应类反应势垒与速率常数的精确计算

汪必耀², 谈宁馨², 姚倩¹, 李泽荣¹, 李象远²

1 四川大学化学学院, 成都 610064;
2 四川大学化学工程学院, 成都 610065

收稿日期:2012-07-31 修回日期:2012-09-05 发布日期:2012-11-14
通讯作者: 李泽荣 E-mail:lizerong@scu.edu.cn
基金资助:
国家自然科学基金(20973118, 91016002)资助项目

Accurate Calculation of the Reaction Barriers and Rate Constants of the Pyrolysis of Alkyl Radicals in the β Position Using the Isodesmic Reaction Method

WANG Bi-Yao², TAN Ning-Xin², YAO Qian¹, LI Ze-Rong¹, LI Xiang-Yuan²

1 College of Chemistry, Sichuan University, Chengdu 610064, P. R. China;
2 College of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China

Received:2012-07-31 Revised:2012-09-05 Published:2012-11-14
Supported by:
The project was supported by the National Natural Science Foundation of China (20973118, 91016002)

摘要/Abstract

摘要：

提出反应类等键方法并用于高温燃烧机理中一类重要反应——烷基自由基β位裂解反应的反应势垒和速率常数的精确校正计算. 通过10种不同从头算水平对类反应中5个代表反应的反应势垒的计算发现, 用反应类等键反应方法和直接从头算方法获得的5 个代表反应的反应势垒最大绝对偏差的平均值分别为5.32 和16.16 kJ·mol^-1, 表明反应类等键反应方法计算的反应势垒对不同水平从头算方法的依赖性小, 可在较低从头算水平计算得到精确的反应势垒, 解决大分子体系反应势垒的精确计算问题. 此外应用反应类等键反应方法在BHandHLYP/cc-pVDZ 从头算水平计算了3 个代表反应的速率常数, 并与文献报道的实验值进行了比较, 其在500-2000 K温度区间内计算速率常数与实验速率常数中较大值与较小值的比值k_max/k_min的平均值为1.67, 最大值也仅有2.49. 表明应用反应类等键反应方法在较低从头算水平即可对同类反应的速率常数进行精确计算.最后在BHandHLYP/cc-pVDZ从头算水平用反应类等键反应方法计算了13个烷基自由基β位裂解反应的速率常数.

关键词: 反应类等键反应方法, 烷基β位裂解反应, 反应势垒, 速率常数

Abstract:

The isodesmic reaction method is proposed for the accurate calculation of the reaction barriers and rate constants for an important class of reactions in the high-temperature combustion mechanism: the pyrolysis of alkyl radicals in the β position. The reaction barriers were calculated for a representative set of five reactions by two schemes: the first scheme is to calculate the reaction barriers directly from approximate ab initio calculations; and the second scheme is to correct the reaction barriers from the first scheme using the isodesmic reaction method. Ten different levels of ab initio calculations were used, and the absolute average maximum deviations of the reaction barriers by the isodesmic reaction method and direct ab initio calculations were 5.32 and 16.16 kJ·mol^-1, respectively, indicating that the isodesmic reaction method does not significantly depend on the level of ab initio theory used. The rate constants of the three representative reactions in the temperature range of 500-2000 K were calculated by the isodesmic reaction method. The average and maximum values of k_max/k_min between the calculated and experimental values were 1.67 and 2.49, respectively. Therefore, the isodesmic reaction method is efficient and reliable for the calculation of the reaction barriers and rate constants of reactions in a class at a modest level of ab initio theory.

Key words: Reaction class isodesmic reaction method, Pyrolysis reaction of β alkyl, Reaction barrier, Rate constant

汪必耀, 谈宁馨, 姚倩, 李泽荣, 李象远. 烷基自由基β位裂解反应类反应势垒与速率常数的精确计算[J]. 物理化学学报, 2012, 28(12), 2824-2830. doi: 10.3866/PKU.WHXB201209053

WANG Bi-Yao, TAN Ning-Xin, YAO Qian, LI Ze-Rong, LI Xiang-Yuan. Accurate Calculation of the Reaction Barriers and Rate Constants of the Pyrolysis of Alkyl Radicals in the β Position Using the Isodesmic Reaction Method[J]. Acta Phys. -Chim. Sin. 2012, 28(12), 2824-2830. doi: 10.3866/PKU.WHXB201209053

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201209053

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I12/2824

参考文献

(1) Lu, T. F.; Law, C. K. Combust. Flame 2006, 144, 24. doi: 10.1016/j.combustflame.2005.02.015
(2) Pepiot-Desjardins, P.; Pitsch, H. Combust. Flame 2008, 154, 67.doi: 10.1016/j.combustflame.2007.10.020
(3) Curran, H. J.; Gaffuri, P.; Pitz,W. J. Combust. Flame 1998, 114,149. doi: 10.1016/S0010-2180(97)00282-4
(4) Curran, H. J.; Gaffuri, P.; Pitz,W. J. Combust. Flame 2002, 129,253. doi: 10.1016/S0010-2180(01)00373-X
(5) Knyazev, V. D.; Bencsura, A.; Dubinsky, I. A.; Gutman, D.;Senkan, S. M. Proc. Combust. Inst. 1994, 25, 817.
(6) Knyazev, V. D.; Dubinsky, I. A.; Slagle, I. R.; Gutman, D.J. Phys. Chem. 1994, 98, 5279. doi: 10.1021/j100071a018
(7) Knyazev, V. D.; Dubinsky, I. A.; Slagle, I. R.; Gutman, D.J. Phys. Chem. 1994, 98, 11099. doi: 10.1021/j100094a018
(8) Slagle, I. R.; Batt, L.; Gmurczyk, G.W.; Gutman, D.; Tsang,W.J. Phys. Chem. 1991, 95, 7732. doi: 10.1021/j100173a034
(9) Bencsura, A.; Knyazev, V. D.; Xing, S. B.; Slagle, I. R.;Gutman, D. Proc. Combust. Inst. 1992, 24, 629.
(10) Zheng, X. B.; Blowers, P. Ind. Eng. Chem. Res. 2006, 45, 530.doi: 10.1021/ie0508942
(11) Truong, T. N. J. Chem. Phys. 2000, 113, 4959.
(12) Huynh, L. K.; Ratkiewicz, A.; Truong, T. N. J. Phys. Chem. A2006, 110, 473. doi: 10.1021/jp051280d
(13) Muszynska, M.; Ratkiewicz, A.; Huynh, L. K.; Truong, T. N.J. Phys. Chem. A 2009, 113, 8327. doi: 10.1021/jp903762x
(14) Bankiewicz, B.; Huynh, L. K.; Ratkiewicz, A.; Truong, T. N. J. Phys. Chem. A 2009, 113, 1564. doi: 10.1021/jp808874j
(15) Zhang, S.W.; Truong, T. N. J. Phys. Chem. A 2003, 107, 1138.doi: 10.1021/jp021265y
(16) Kungwan, N.; Truong, T. N. J. Phys. Chem. A 2005, 109, 7742.doi: 10.1021/jp051799+
(17) Huynh, L. K.; Truong, T. N. Theor. Chem. Acc. 2008, 120, 107.doi: 10.1007/s00214-007-0311-9
(18) Hehre,W. J.; Ditchfield, R.; Radom, L.; Pople, J. A. J. Am. Chem. Soc. 1970, 92, 4796. doi: 10.1021/ja00719a006
(19) Radom, L.; Hehre,W. J.; Pople, J. A. J. Am. Chem. Soc. 1971,93, 289. doi: 10.1021/ja00731a001
(20) Wiberg, K. B.; Ochterski, J.W. J. Comput. Chem. 1997, 18, 108.
(21) Gonzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523.doi: 10.1021/j100377a021
(22) Truhlar, D. G. Chem. Phys. Lett. 1998, 294, 45. doi: 10.1016/S0009-2614(98)00866-5
(23) Halkier, A.; Helgaker, T.; Jorgensen, P. J. Chem. Phys. Lett.1999, 302, 437. doi: 10.1016/S0009-2614(99)00179-7
(24) De Lara-Castells, M. P.; Krems, R. V.; Buchachenko, A. A. J. Chem. Phys. 2001, 115, 10438. doi: 10.1063/1.1415078
(25) Huh, S. B.; Lee, J. S. J. Chem. Phys. 2003, 118, 3035. doi: 10.1063/1.1534091
(26) Hwang, R.; Park, Y. C.; Lee, J. S. Theor. Chem. Acc. 2006, 115,54. doi: 10.1007/s00214-005-0675-7
(27) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03,Revision B.01; Gaussian Inc.: Pittsburgh, PA, 2003.
(28) Duncan,W. T.; Bell, R. L.; Truong, T. N. J. Comput. Chem.1998, 19, 1039.
(29) Eckart, C. Phys. Rev. 1930, 35, 1303. doi: 10.1103/PhysRev.35.1303
(30) Morganroth,W. E.; Calvert, J. G. J. Am. Chem. Soc. 1966, 88,5387. doi: 10.1021/ja00975a004
(31) Knyazev, V. D.; Slagle, I. R. J. Phys. Chem. 1996, 100, 5318.doi: 10.1021/jp952229k
(32) Kerr, J. A.; Trotman-Dickenson, A. F. J. Chem. Soc. 1960, 323,1602.
(33) Gierczak, T.; Gawlowski, J.; Niedzielski, J. React. Kinet. Catal. Lett. 1988, 36, 434.
(34) Tsang,W. J. Am. Chem. Soc. 1985, 107, 2872. doi: 10.1021/ja00296a007
(35) Lin, M. C.; Laidler, K. J. Can. J. Chem. 1967, 45, 1315.
(36) Gang, J.; Pilling, M. J.; Robertson, S. H. J. Chem. Soc. Faraday Trans. 1997, 93, 1481. doi: 10.1039/a607566e
(37) Metcalfe, E. L.; Trotman-Dickenson, A. F. J. Chem. Soc. 1960,980, 5072.
(38) Slater, D. H.; Collier, S. S.; Calvert, J. G. J. Am. Chem. Soc.1968, 90, 268. doi: 10.1021/ja01004a010
(39) Douhou, S.; Perrin, D.; Martin, R. J. Chim. Phys. 1994, 91,1628.

[1]	苏敏仪,刘慧思,林海霞,王任小. 应用机器学习方法构建药物分子解离速率常数的预测模型[J]. 物理化学学报, 2020, 36(1): 1907006 - .
[2]	姚倩,彭莉娟,李泽荣,李象远. 烷烃与氢过氧自由基氢提取反应类反应能垒与速率常数的精确计算[J]. 物理化学学报, 2017, 33(4): 763 -768 .
[3]	于洪晶,夏文文,宋立国,丁杨,郝宇,康利强,潘新祥,姚丽. 甲基肼自由基在高温燃烧分解反应下的非谐振效应[J]. 物理化学学报, 2017, 33(11): 2207 -2218 .
[4]	张田雷,杨晨,凤旭凯,王竹青,王睿,刘秋丽,张鹏,王文亮. HS+HO₂气相反应机理及主通道速率常数的理论研究[J]. 物理化学学报, 2016, 32(3): 701 -710 .
[5]	杜鸟锋,甯红波,李泽荣,张其翼,李象远. 1, 3-丁二烯热裂解的动力学计算与模型研究[J]. 物理化学学报, 2016, 32(2): 453 -464 .
[6]	丁杨,宋立国,余忆玄,姚丽,林圣贤. 丁酸甲酯单分子解离的非谐振效应[J]. 物理化学学报, 2016, 32(11): 2685 -2692 .
[7]	李尚俊, 谈宁馨, 姚倩, 李泽荣, 李象远. 过氧烷基自由基分子内氢迁移反应类速率常数的计算[J]. 物理化学学报, 2015, 31(5): 859 -865 .
[8]	许琼, 张田雷, 吕文彬, 王睿, 王志银, 王文亮, 王竹青. 单分子水对H₂O₂+Cl气相反应影响的理论研究[J]. 物理化学学报, 2014, 30(6): 1061 -1070 .
[9]	胡仁志, 谢品华, 张群, 司福祺, 陈旸. C₂（a³П_u）自由基与含硫小分子反应的温度效应[J]. 物理化学学报, 2014, 30(5): 797 -802 .
[10]	张田雷, 王渭娜, 刘畅, 吕娜, 陈妙, 郭莎, 王文亮. 反式2-甲基-2-丁烯酸甲酯与臭氧反应机理的计算研究[J]. 物理化学学报, 2013, 29(11): 2313 -2320 .
[11]	曹佳, 王文亮, 高楼军, 付峰. CH₃SO₃裂解反应的机理和热力学性质[J]. 物理化学学报, 2013, 29(06): 1161 -1167 .
[12]	胡仁志, 谢品华, 张群, 司福祺, 陈旸. C₂(X¹Σ_g⁺)自由基与不饱和碳氢化合物反应的温度效应[J]. 物理化学学报, 2013, 29(04): 683 -688 .
[13]	冯丽霞, 靳玲侠, 王渭娜, 王文亮. C₂H₃与CH₃F氢抽提反应机理与动力学性质[J]. 物理化学学报, 2012, 28(07): 1623 -1629 .
[14]	李晓艳, 刘群, 郑世钧, 孟令鹏. HOSO+NO反应的机理及动力学[J]. 物理化学学报, 2011, 27(03): 564 -570 .
[15]	崔凤超, 于洪波, 王钦, 叶宛丽, 刘靖尧. CH₃OCF₂CF₂OCH₃+Cl的反应机理及动力学性质[J]. 物理化学学报, 2011, 27(02): 337 -342 .

烷基自由基β位裂解反应类反应势垒与速率常数的精确计算

Accurate Calculation of the Reaction Barriers and Rate Constants of the Pyrolysis of Alkyl Radicals in the β Position Using the Isodesmic Reaction Method

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0