范德华复合物Kr-C2H2的势能面和振转光谱的理论研究

doi:10.7503/cjcu20190254

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (8): 1649.doi: 10.7503/cjcu20190254

范德华复合物Kr-C₂H₂的势能面和振转光谱的理论研究

白旭, 韩超英, 朱华

四川大学化学学院, 成都 610064

收稿日期:2019-05-05 修回日期:2019-07-23 出版日期:2019-08-10 发布日期:2019-07-12
通讯作者: 朱华,女,博士,教授,主要从事分子光谱研究.E-mail:zhuhua@scu.edu.cn E-mail:zhuhua@scu.edu.cn
基金资助:
国家自然科学基金（批准号：21373139）和四川省应用基础项目（批准号：2018JY0712）资助.

Theoretical Studies of the Potential Energy Surface and Rovibrational Spectra for Kr-C₂H₂

BAI Xu, HAN Chaoying, ZHU Hua

College of Chemistry, Sichuan University, Chengdu 610064, China

Received:2019-05-05 Revised:2019-07-23 Online:2019-08-10 Published:2019-07-12
Supported by:
Supported by the National Natural Science Foundation of China(No.21373139) and the Sichuan Province Application Foundation, China(No.2018JY0712).

摘要/Abstract

摘要： 采用[CCSD（T）]-F12方法和aug-cc-pVTZ基组，同时引入中心键函数（3s3p2d1f1g）构建了Kr-C₂H₂体系的高精度四维势能面.在构建势能面时考虑了分子间的振动方式及C₂H₂单体内的ν₁对称伸缩和ν₃反对称伸缩振动.将计算得到的四维势能面在Q₁方向和Q₃方向分别做积分得到C₂H₂单体分别处于振动基态和（ν₁，ν₃）=（1，1）激发态的平均势能面.计算结果表明，这2个平均势能面均存在2个等价的T型全局极小值和2个等价线性极小值.全局极小值的几何构型位于R=0.41 nm，θ=65.6°/114.4°，势阱深度为151.88 cm^-1.对径向部分采用离散变量表象法（DVR），角度部分采用有限基组表象法（FBR），并结合Lanczos循环算法计算了Kr-C₂H₂的振转能级和束缚态.计算结果表明，复合物在（ν₁，ν₃）=（1，1）区域的带心位移为-1.48 cm^-1，表现为红移，与实验值-1.38 cm^-1很接近；计算得到的红外跃迁频率也与实验值相吻合，说明得到的从头算势能面具有高精度.

关键词: Kr-C₂H₂, 势能面, 振转光谱, 分子内振动激发

Abstract: A new four-dimensional(4D) potential energy surface(PES) for the Kr-C₂H₂ complex including the Q₁ and Q₃ normal modes for the ν₁ symmetric stretching vibration and ν₃ antisymmetric stretching vibration of C₂H₂ was studied. The PES was calculated at the coupled-cluster singles and doubles with noniterative inclusion of connected triples[CCSD(T)] -F12 level with augmented correlation-consistent polarized-valence quadruplet-zeta(aug-cc-pVTZ) basis set plus the midpoint bond function(3s3p2d1f1g). Two averaged vibrational potential energy surfaces of C₂H₂ at both the vibrational ground and (ν₁,ν₃)=(1,1) excited states were generated from the integration of the four-dimensional potential over the Q₁ and Q₃ coordinates. The averaged potential energy surfaces have two equivalent T-shaped global minima, two equivalent local linear minima as well as three saddle points between the minima. The global minima are located at R=0.41 nm and θ=65.6°/114.4° with a well depth of 151.88 cm^-1. The radial discrete variable representation(DVR)/angular finite basis representation(FBR) method and Lanczos algorithm were employed to calculate the rovibrational energy levels and bound states. The calculated vibrational band origin for the Kr-C₂H₂ complex is red shifted by -1.48 cm^-1, which is closed to the observed value of -1.38 cm^-1. The infrared spectra agree well with the experiment data. The good agreement with the experiment values verifies the high quality of ab initio PESs.

Key words: Kr-C₂H₂, Potential energy surface, Rovibrational spectra, Intramolecular vibrational excitation

中图分类号:

O641

TrendMD:

白旭, 韩超英, 朱华. 范德华复合物Kr-C₂H₂的势能面和振转光谱的理论研究. 高等学校化学学报, 2019, 40(8): 1649.

BAI Xu, HAN Chaoying, ZHU Hua. Theoretical Studies of the Potential Energy Surface and Rovibrational Spectra for Kr-C₂H₂. Chem. J. Chinese Universities, 2019, 40(8): 1649.

参考文献 45

[1]	Goldman A., Murcray F. J., Blatherwick R. D., Gillis J. R,. Bonomo F. S., Murcray F. H., J. Geophys. Research:Oceans, 1981, 86(C12), 12143-12146
[2]	Chen F., Judge D. L., Robert Wu C. Y., Caldwell J., White H. P., Wagener R., J. Geophys. Research:Planets, 1991, 96(E2), 17519-17527
[3]	Lellouch E., Bézard B., Moses J. I., Davis G. R., Drossart P., Feuchtgruber H., Icarus, 2002, 159(1), 112-131
[4]	Deleon R. L., Muenter J. S., J. Chem. Phys., 1980, 72(4), 6020-6023
[5]	Ohshima Y., Iida M., Endo Y., Chem. Phys. Lett., 1989, 161(3), 202-206
[6]	Liu Y., Jäger W., J. Mol. Spectrosc., 2001, 205(1), 177-182
[7]	Liu Y., Jäger W., Phys. Chem. Chem. Phys., 2003, 5(9), 1744-1751
[8]	Prichard D. G., Muenter J. S., Howard B. J., 42nd Symposium on Molecular Spectroscopy, Ohio State University, Columbus, 1987
[9]	Hu T. A., Prichard D. G., Sun L. H., Muenter J. S., Howard B. J., J. Mol. Spectrosc., 1992, 153(1/2), 486-496
[10]	Bemish R. J., Block P. A., Pedersen L. G., Yang W., Miller R. E., J. Chem. Phys., 1993, 99(11), 8585-8598
[11]	Ohshima Y., Matsumot Y., Takami M., Kuchitsu K., J. Chem. Phys., 1993, 99(11), 8385-8397
[12]	Milce A. P., Heard D. E., Miller R. E., Orr B., J. Chem. Phys. Lett., 1996, 250(1), 95-103
[13]	Macko P., Lauzin C., Herman M., Chem. Phys. Lett., 2007, 445(4-6), 113-116
[14]	Lauzin C., Didriche K., Macko P., Demaison J., Liévin J., Herman M., J. Phys. Chem. A, 2009, 113(11), 2359-2365
[15]	Lauzin C., Didriche K., Phys. Chem. Chem. Phys., 2011, 13(2), 751-754
[16]	Didriche K., Foldes T., Lauzin C., Golebiowski D., Liévin J., Herman M., Mol. Phys., 2012, 110(21/22), 2781-2796
[17]	Thomley A. E., Hutson J. M., Chem. Phys. Lett., 1992, 198(1/2), 1-8
[18]	Bone R. G. A., J. Phys. Chem., 1994, 98(12), 3126-3138
[19]	Tao F. M., Drucker S., Klemperer W., J. Chem. Phys., 1995, 102(19), 7289-7297
[20]	Yang M., Alexander M. H., Werner H. J., Bemish R. J., J. Chem. Phys., 1996, 105(23), 10462-10471
[21]	Munteanu C. R., Fernandez B., J. Chem. Phys., 2005, 123(1), 8471-8480
[22]	Lauzin C., Coudert L. H., Herman M., Liévin J., J. Phys. Chem. A, 2013, 117(50), 13767-13774
[23]	Lauzin C., Cauet E., Demaison J., Herman M., Stoll H., Liévin J., Mol. Phys., 2012, 110(21/22), 2751-2760
[24]	Ran H., Zhou Y. Z., Xie D. Q., J. Chem. Phys., 2007, 126(20), 204304
[25]	Ran H., Xie D. Q., J. Chem. Phys., 2008, 128(12), 124323
[26]	Li H., Blinov N., Roy P. N., Roy R. J. L., J. Chem. Phys., 2009, 130(14), 144305
[27]	Li H., Ma T. Y., J. Chem. Phys., 2012, 137(23), 234310
[28]	Shang J., Yuan T., Zhu H., Chem. Phys. Lett., 2016, 648, 147-151
[29]	Shang J., Yuan T., Zhu H., Theor. Chem. Acc., 2016, 135(1), 1-8
[30]	Hong Q., Qin M., Zhu H., Acta Chim. Sinica, 2018, 76(2), 138-142
[31]	Adler T. B., Knizia G., Werner H. J., J. Chem. Phys., 1992, 127(22), 221106
[32]	Knizia G., Adler T. B., Werner H. J., J. Chem. Phys., 2009, 130(5), 054104
[33]	Echave J., Clary D. C., Chem. Phys. Lett., 1992, 190(3/4), 225-230
[34]	Wei H., Carrington T., J. Chem. Phys., 1992, 97(5), 3029-3037
[35]	Pedersen T. B., Fernandez B., Koch H., Makarewicz J., J. Chem. Phys., 2001, 115(18), 8431-8439
[36]	Boys S. F., Bernardi F., Mol. Phys., 1970, 19(4), 553-566
[37]	Werner H. J., Knowle P. J., Amos R. D., Berning A., Cooper D. L., Deegan M. J. O., Dobbyn A. J., Eckert F., Elbert S. T., Hampel C., Lindh R., Lloyd A. W., Meyer W., Nicklass A., Peterson K., Pitzer R., Stone A. J., Taylor P. R., Mura M. E., Pulay P., Schutz M., Stoll H., Thoorstcinsso T., MOLPRO, Version 2000.1, 2000(http://www.molpro.net)
[38]	Tennyson J., Sutcliffe B. T., Mol. Phys., 1984, 51(4), 887-906
[39]	Miller S., Tennyson J., J. Mol. Spectrosc., 1988, 128(2), 530-539
[40]	Lin S. Y., Guo H., J. Chem. Phys., 2002, 117(11), 5183-5191
[41]	Guo H., Chen R. Q., Xie D. Q., J. Theor. Comp. Chem., 2000, 1(1), 567-574
[42]	Colbert D. T., Miller W. H., J. Chem. Phys., 1992, 96(3), 1982-1991
[43]	Lill J. V., Parker G. A., Light J. C., Chem. Phys. Lett., 1982, 89(6), 483-489
[44]	Lanczos C. J., Res. Natl. Bur. Stand., 1950, 45(4), 255-275
[45]	Yu H. G., J. Chem. Phys., 2002, 117(18), 8190-8196

范德华复合物Kr-C₂H₂的势能面和振转光谱的理论研究

Theoretical Studies of the Potential Energy Surface and Rovibrational Spectra for Kr-C₂H₂

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 45

相关文章 15

编辑推荐

Metrics

本文评价

[1]	安丰, 胡茜茜, 谢代前. 三原子分子非绝热传能动力学的研究进展[J]. 高等学校化学学报, 2021, 42(7): 2103.
[2]	商辰尧, 张东辉. 基本不变量神经网络解析梯度方法的研究[J]. 高等学校化学学报, 2021, 42(7): 2146.
[3]	曲泽星, 高加力. 多组态密度泛函理论及透热与绝热势能面的构建[J]. 高等学校化学学报, 2015, 36(11): 2236.
[4]	张志红, 雷鹏. 准经典轨线方法对Ca+CD₃I→CaI+CD₃同位素效应的动力学研究[J]. 高等学校化学学报, 2013, 34(6): 1450.
[5]	高斯萌, 贺海鹏, 丁益宏. SnAl₄^-和PbAl₄^-: 新型平面四配位分子[J]. 高等学校化学学报, 2013, 34(1): 185.
[6]	慈成刚, 段雪梅, 刘靖尧, 孙家钟. 乙醇醛光解离机理的理论研究[J]. 高等学校化学学报, 2011, 32(7): 1588.
[7]	邵长斌, 金林, 丁益宏. B₄O分子异构化稳定性的理论研究[J]. 高等学校化学学报, 2010, 31(2): 348.
[8]	谢长建, 陈容, 朱华, 谢代前. Ne-CO₂的从头算势能面及微波光谱[J]. 高等学校化学学报, 2009, 30(9): 1851.
[9]	张文斌, 石国升, 丁益宏, 孙家锺. SnCNN: 一个包含SnC三重键的分子[J]. 高等学校化学学报, 2009, 30(7): 1427.
[10]	石国升, 丁益宏. H₂NO^·自由基和顺-2-丁烯反应机理的理论研究[J]. 高等学校化学学报, 2009, 30(2): 382.
[11]	周中军, 刘慧玲, 黄旭日, 孙家锺. 预测[C,O,S]体系的稳定异构体[J]. 高等学校化学学报, 2008, 29(8): 1641.
[12]	迟绍明,王宁,马丽英,方芳,田国才,李国宝,徐四川 . NO₃^-+Cl₂→ClONO₂+Cl^-反应势能面和势能阱[J]. 高等学校化学学报, 2008, 29(6): 1228.
[13]	赵晓雷, 姬越蒙, 刘靖尧, 李泽生. NCO自由基与O和N反应的理论研究[J]. 高等学校化学学报, 2008, 29(4): 809.
[14]	张志红,陈茂笃,丛书林 . 基态钙原子与二氯甲烷反应的动力学研究[J]. 高等学校化学学报, 2008, 29(3): 596.
[15]	王嵩 ,于健康 ,丁大军 ,孙家锺 . H+HCNO反应势能面的理论研究[J]. 高等学校化学学报, 2008, 29(2): 365.