氯代苯阳离子的密度泛函理论研究

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (7): 1446.

氯代苯阳离子的密度泛函理论研究

程建波¹, 刘怀成¹, 李文佐¹, 李庆忠¹, 于健康^1,2, 宫宝安¹, 孙家锺^1,2

1. 烟台大学化学生物理工学院, 烟台 264005;
2. 吉林大学理论化学计算国家重点实验室, 长春 130023

收稿日期:2009-10-12 出版日期:2010-07-10 发布日期:2010-07-10
通讯作者: 程建波, 男, 博士, 教授, 主要从事量子化学计算研究. E-mail: jbcheng@ytu.edu.cn; 李文佐, 男, 博士, 副教授, 主要从事量子化学计算研究. E-mail: liwenzuo2004@126.com
基金资助:
国家自然科学基金(批准号: 20473029)、超分子结构与材料国家重点实验室(吉林大学)开放基金(批准号: SKLSSM200713, SKLSSM200909)和烟台大学博士科研基金(批准号: HY05B30, HY05B36)资助.

Density Functional Theory Study on the Chlorinated Benzenes Cations

CHENG Jian-Bo^1*, LIU Huai-Cheng¹, LI Wen-Zuo^1*, LI Qing-Zhong¹, YU Jian-Kang^1,2, GONG Bao-An¹, SUN Chia-Chung^1,2

1. Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, China;
2. State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China

Received:2009-10-12 Online:2010-07-10 Published:2010-07-10
Contact: CHENG Jian-Bo. E-mail: jbcheng@ytu.edu.cn; LI Wen-Zuo. E-mail: liwenzuo2004@126.com
Supported by:
国家自然科学基金(批准号: 20473029)、超分子结构与材料国家重点实验室(吉林大学)开放基金(批准号: SKLSSM200713, SKLSSM200909)和烟台大学博士科研基金(批准号: HY05B30, HY05B36)资助.

摘要/Abstract

摘要：

采用B3LYP方法及6-311G(d,p)和6-311+G(d,p) 基组, 对12种氯代苯阳离子进行了理论研究, 优化其电子基态的结构, 计算了对应分子的垂直电离势(VIP)和绝热电离势(AIP). 依据Jahn-Teller理论, 确定了1,3,5-C₆H₃Cl₃⁺和C₆Cl₆⁺离子分别具有C_2v(²B₁)和D_2h(²B_2g)结构(对应分子分别为D_3h和D_6h结构). 其余10个离子的构型的对称点群与对应分子相同, 但构型参数值有明显差别. 用B3LYP方法计算的各氯代苯分子的垂直电离势和绝热电离势与实验值符合得很好.

关键词: 氯代苯阳离子; 电子基态结构; 电离势; B3LYP方法

Abstract:

Twelve chlorinated benzenes cations were studied by the B3LYP method in conjunction with the 6-311G(d,p) and 6-311+G(d,p) basis sets. The ground-state geometries of these cations were predicted and the vertical ionization potentials(VIPs) and adiabatic ionization potentials(AIPs) of the corresponding molecules were calculated. The 1,3,5-C₆H₃F₃⁺ and C₆F₆⁺ ions are the Jahn-Teller active species, and they are predicted to have C_2v and D_2h structures, in contrast with the D_3h and D_6h structures of their parent molecules, respectively. Though other ten cations have same symmetry with their respective parent molecules, the geometric parameters of cations are different with the molecules. The B3LYP calculations predict vertical and adiaba-tic ionization potential values of the chlorinated benzene molecules in good agreement with the available experimental values.

Key words: Chlorinated benzenes cation; Geometry; Ionization potential; B3LYP method

TrendMD:

程建波, 刘怀成, 李文佐, 李庆忠, 于健康, 宫宝安, 孙家锺. 氯代苯阳离子的密度泛函理论研究. 高等学校化学学报, 2010, 31(7): 1446.

CHENG Jian-Bo*, LIU Huai-Cheng, LI Wen-Zuo*, LI Qing-Zhong, YU Jian-Kang, .... Density Functional Theory Study on the Chlorinated Benzenes Cations. Chem. J. Chinese Universities, 2010, 31(7): 1446.

参考文献

[1]Anderson S. L., Rider D. M., Zare R. N.. Chem. Phys. Lett.[J], 1982, 93: 11—15
[2]Walter K., Scherm K., Boesl U.. J. Phys. Chem.[J], 1991, 95: 1188—1194
[3]Szczepanski J., Personette W., Pellow R., Chandrasekhar T. M., Roser D., Cory M., Zerner M., Vala M.. J. Chem. Phys.[J], 1992, 96: 35—43
[4]Wright T. G., Panov S. I., Miller T.A.. J. Chem. Phys.[J], 1995, 102: 4793—4803
[5]Potts A. W., Edvardsson D., Karlsson L., Holland D. M. P., MacDonald M. A., Hayes M. A., Maripuu R., Siegbahn K., Niessen W.. Chem. Phys.[J], 2000, 254: 385—405
[6]Anand R., Hofstein J. D., LeClaire J. E., Johnson P. M., Cossart-Magos C.. J. Phys. Chem. A[J], 1999, 103: 8927—8934
[7]Lembach G., Brutschy B.. Chem. Phys. Lett.[J], 1997, 273: 421—428
[8]Kwon C. H., Kim H. L., Kim M. S.. J. Chem. Phys.[J], 2002, 116: 10361—10371
[9]Youn Y. Y., Kwon C. H., Choe J. C., Kim M. S.. J. Chem. Phys.[J], 2002, 117: 2538—2545
[10]Asselin P., Gouzerh A., Piuzzi F., Dimicoli I.. Chem. Phys.[J], 1993, 175: 387—398
[11]Asselin P., Piuzzi F., Le Calvé J., Mons M., Dimicoli I.. Chem. Phys.[J], 1994, 181: 271—279
[12]Urbain P., Leyh B., Remacle F., Lorquet A. J., Flammang R., Lorquet J.C.. J. Chem. Phys.[J], 1999, 110: 2911—2921
[13]Rušcic′ B., Klaslnc L., Wolf A., Knop J. V.. J. Phys. Chem.[J], 1981, 85: 1486—1489
[14]Rušcic′ B., Klaslnc L., Wolf A., Knop J. V.. J. Phys. Chem.[J], 1981, 85: 1490—1495
[15]Rušcic′ B., Klaslnc L., Wolf A., Knop J. V.. J. Phys. Chem.[J], 1981, 85: 1495—1497
[16]Maier J. P., Marthaler O.. Chem. Phys.[J], 1978, 32: 419—427
[17]Watanabe K., Nakayama T., Mottl J.. J. Quant. Spectrosc. Radiat. Transfer.[J], 1962, 2: 369—382
[18]Price W. C., Walsh A. D.. Proc. Roy. Soc.[J], 1947, A191: 22—31
[19]Zakrzewski V. G., Ortiz J. V.. J. Mol Struct(Theochem.)[J], 1996, 388: 351—357
[20]Klippenstein S. J.. Int. J. Mass Spectrom. Ion Processes[J], 1997, 167/168: 235—257
[21]Li W. Z., Huang M. B.. Chem. Phys. Lett.[J], 2005, 405: 1—9
[22]Yu S. Y., Huang M. B.. Chem. Phys.[J], 2006, 328: 291—298
[23]Yu S. Y., Huang M. B.. J. Mol Struct(Theochem.)[J], 2007, 822: 48—56
[24]LI Wen-Zuo(李文佐), HUANG Ming-Bao(黄明宝). Acta Phys. Chim. Sin.(物理化学学报), 2004, 20: 21—26
[25]LI Wen-Zuo(李文佐), HUANG Ming-Bao(黄明宝). Acta Chim. Sin.(化学学报), 2004, 62: 883—887
[26]Hohenberg P., Kohn W.. Phys. Rev.[J], 1964, 136: B864—B871
[27]Feller D.. J. Chem. Phys.[J], 1990, 93: 579—589
[28]Becke A. D.. J. Chem. Phys.[J], 1993, 98: 5648—5652
[29]Lee C., Yang W., Parr R. G.. Phys. Rev.[J], 1988, 37: 785—789
[30]Hehre W. J., Radom L., Schleyer P. v. R., Pople J. A.. Ab Initio Molecular Orbital Theory[M], New York: Wiley, 1986
[31]Cederbaum L. S.. J. Phys. B[J], 1975, 8: 290—303
[32]Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A., Vreven T. Jr., Kudin K. N., Burant J. C., et al.. Gaussian 03, Revision B.03[CP], Pittsburgh, PA: Gaussian, Inc., 2003
[33]Martin J. M. L., Francois J. P., Gijbels R.. J. Comput. Chem.[J], 1989, 10: 346—357