二核铪氧簇Hf2On-/0(n=1~6)的电子性质与结构演化的理论研究

doi:10.6023/A16090505

摘要/Abstract

采用密度泛函理论（DFT）与耦合簇[CCSD（T）]相结合的计算方法对一系列二核铪氧簇合物Hf₂O_n^-/0（n=1～6）的电子结构进行了系统研究.通过密度泛函理论（DFT）计算对体系的势能面进行广泛的搜索，寻找能量最低的结构.采用广义Koopmans定理计算垂直电子逸出能（VDEs）并模拟阴离子光电子谱（PES）.通过理论研究阐明了二核铪氧簇Hf₂O_n^-/0（n=1～6）结构演化规律，并利用分子轨道分析对二核铪氧簇Hf₂O_n^-（n=1～4）的化学成键和顺序氧化进行解释.自旋密度分析显示：除Hf₂O₅中性簇之外，其它富氧簇都存在多种类型的氧自由基：氧自由基、双自由基或超氧自由基.此外，研究发现Hf₂O₃中性簇中的定域Hf²⁺位容易与分子氧O₂反应形成Hf₂O₅中性簇；Hf₂O₄^-/0簇合物与分子O₂作用形成Hf₂O₆^-/0簇合物，Hf₂O₄^-/0簇合物可以作为潜在的分子模型研究氧分子在铪氧化物上的活化.

关键词: 铪氧簇合物, 密度泛函理论, 耦合簇理论, 自由基, 模拟光电子谱

Extensive density functional theoretical (DFT) and ab initio[CCSD (T)]calculations were combined to investigate the geometric and electronic structure of a series of dinuclear hafnium oxide clusters,Hf₂O_n^-/0(n=1~6).DFT calculations were performed to search for the lowest energy structures for both the anionic clusters and the neutral counterparts.The search for the global minima was performed using analytical gradients with the Stuttgart relativistic small core potential and the valence basis sets augmented with two f-type and one g-type polarization functions for Hf and the aug-cc-pVTZ basis set for oxygen.The relative energies of the low-lying structures (within ca.0.35 eV) were further evaluated via single-point calculations at the coupled cluster[CCSD (T)]level with the Hf/Stuttgart+2f1g/O/aug-cc-pVTZ basis sets at the B3LYP geometries.Generalized Koopmans' theorem (GKT) was applied to predict VDEs and simulate the anion photoelectron spectra (PES).The trends of structural evolution and the behavior of sequential oxidation of the Hf₂O_n^-(n=1~6) clusters were observed.For the anionic species,starting from the C_2v triangular structure Hf₂O^-,the next O atom in the Hf₂O₂^- cluster was again bridge-bonded,forming a rhombus structure.The third O atom occupied the terminal site.The fourth O atom favored the bridging site and the fifth O atom occupied the terminal site.In Hf₂O₆^-,the additional O atom was bonded to a terminal site.Molecular orbital analyses were performed to elucidate the chemical bonding and the structural evolution in Hf₂O_n^-(n=1~4) clusters.Spin density analyses revealed oxygen radical,diradical and superoxide characters in the oxygen-rich clusters,except for the singlet Hf₂O₅ cluster.We showed that Hf₂O₃ contains a localized Hf²⁺ site,which can readily react with O₂ to form the Hf₂O₅ cluster.The Hf₂O₆^- and Hf₂O₆ clusters,which can be viewed to be formed by the interaction of Hf₂O₄^-/0 and O₂,may be utilized as molecular models to understand dioxygen activation on Hf₂O₄^- and Hf₂O₄ clusters.

Key words: hafnium oxide cluster, DFT, CCSD (T), radical, simulated PES

引用此文

陈仕芳, 陈文杰, 王彬, 章晓斌, 黄昕, 章永凡. 二核铪氧簇Hf₂O_n^-/0(n=1~6)的电子性质与结构演化的理论研究[J]. 化学学报, 2016, 74(12): 1009-1017.

Chen Shifang, Chen Wenjie, Wang Bin, Zhang Xiaobin, Huang Xin, Zhang Yongfan. Theoretical Study on Electronic Properties and Structural Evolution in Hf₂O_n^-/0 (n=1~6) Clusters[J]. Acta Chim. Sinica, 2016, 74(12): 1009-1017.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Salem, I. Catal. Rev. 2003, 45, 205.
[2] Ribeiro, M. C.; Jacobs, G.; Linganiso, L.; Azzam, K. G.; Graham, U.M.; Davis, B. H. ACS Catal. 2011, 1, 1375.
[3] Chen, Q. F.; Shi, W. M.; Jiang, D.; Xu, Y.; Wu, D.; Sun, Y. H. Acta Chim. Sinica 2010, 68, 301. (in Chinese). (陈其凤, 史卫梅, 姜东, 徐耀, 吴东, 孙予罕, 化学学报, 2010, 68, 301.)
[4] Ganduglia-Pirovano, M. V.; Hofmann, A.; Sauer, J. Surf. Sci. Rep. 2007, 62, 219.
[5] Reddy, B. M.; Khan, A. Catal. Rev. 2005, 47, 257.
[6] Nie, J.; Lu, Z. H.; Yao, J.; Gui, T.; Chen, X. S. Acta Phys.-Chim. Sin. 2013, 29, 1433. (in Chinese). (聂静, 卢章辉, 姚军, 桂田, 陈祥树, 物理化学学报, 2013, 29, 1433.)
[7] Miyazaki, H.; Matsui, H.; Karuppuchamy, S.; Uchizumi, J.; Ito, S.; Yoshihara, M. Mater. Chem. Phys. 2009, 113, 36.
[8] Böhme, D. K.; Schwarz, H. Angew. Chem. Int. Ed. 2005, 44, 2336.
[9] Wang, J. F.; Jia, J. F.; Ma, L. J.; Wu, H. S. Acta Chim. Sinica 2012, 70, 1643(in Chinese). (王剑锋, 贾建峰, 马丽娟, 武海顺, 化学学报, 2012, 70, 1643.)
[10] Edvinsson, G.; Nylén, C. H. Phys. Scr. 1971, 3, 261.
[11] Rauh, E. G.; Ackermann, R. J. J. Chem. Phys. 1974, 60, 1396.
[12] Lourenço, C.; Michelini, M. C.; Marçalo, J.; Gibson, J. K.; Oliveira, M. C. J. Phys. Chem. A 2012, 116, 12399.
[13] Gong, Y.; Zhou, M. F. Chin. J. Chem. Phys. 2009, 22, 113. (in Chinese). (龚昱, 周鸣飞, 化学物理学报, 2009, 22, 113.)
[14] Chertihin, G. V.; Andrews, L. J. Phys. Chem. 1995, 99, 6356.
[15] Gong, Y.; Zhang, Q.; Zhou, M. F. J. Phys. Chem. A 2007, 111, 3534.
[16] Gong, Y.; Andrews, L.; Bauschlicher, C. W.; Thanthiriwatte, K. S.; Dixon, D. A. Dalton Trans. 2012, 41, 11706.
[17] Gong, Y.; Zhou, M. F. J. Phys. Chem. A 2007, 111, 8973.
[18] Zheng, W.; Bowen, Jr. K. H.; Li, J.; D?bkowska, I.; Gutowski, M. J. Phys. Chem. A 2005, 109, 11521.
[19] Li, X.; Zheng, W.; Buonaugurio, A.; Buytendyk, A.; Bowen, K.; Balasubramanian, K. J. Chem. Phys. 2012, 136, 1591.
[20] Zhai, H. J.; Chen, W. J.; Lin, S. J.; Huang, X.; Wang, L. S. J. Phys. Chem. A 2013, 117, 1042.
[21] Kim, J. B.; Weichman, M. L.; Neumark, D. M. Phys. Chem. Chem. Phys. 2013, 15, 20973.
[22] Woodley, S. M.; Hamad, S.; Mejías, J. A.; Catlow, C. R. A. J. Mater. Chem. 2006, 16, 1927.
[23] Li, S.; Dixon, D. A. J. Phys. Chem. A 2010, 114, 2665.
[24] Fang, Z.; Outlaw, M. D.; Smith, K. K.; Gist, N. W.; Li, S.; Dixon, D. A.; Gole, J. L. J. Phys. Chem. C 2012, 116, 8475.
[25] Fang, Z.; Dixon, D. A. J. Phys. Chem. A 2013, 117, 3539.
[26] Leite Alves, H. W.; Silva, C. C.; Lino, A. T.; Borges, P. D.; Scolfaro, L. M. R.; da Silva, Jr. E. F. Appl. Surf. Sci. 2008, 255, 752.
[27] Brites, V.; Franzreb, K.; Harvey, J. N.; Sayres, S. G.; Ross, M. W.; Blumling, D. E.; Castleman, Jr. A. W.; Hochlaf, M. Phys. Chem. Chem. Phys. 2011, 13, 15233.
[28] Zhao, Y. X.; Wu, X. N.; Wang, Z. C.; He, S. G.; Ding, X. L. Chem. Commun. 2010, 46, 1736.
[29] Zhao, Y. X.; Ding, X. L.; Ma, Y. P.; Wang, Z. C.; He, S. G. Theor. Chem. Acc. 2010, 127, 449.
[30] Lesarri, A.; Suenram, R. D.; Brugh, D. J. Chem. Phys. 2002, 117, 9651.
[31] Suenram, R. D.; Lovas, F. J.; Fraser, G. T.; Matsumura, K. J. Chem. Phys. 1990, 92, 4724.
[32] Zhang, W.; Hou, Z. F. Phys. Status Solidi 2013, 250, 352.
[33] Jonsson, J.; Edvinsson, G.; Taklif, A. G. J. Mol. Spectrosc. 1995, 172, 299.
[34] Kaledin, L. A.; Mccord, J. E.; Heaven, M. C. J. Mol. Spectrosc. 1995, 173, 37.
[35] Haiduke, R. L. A. Chem. Phys. Lett. 2012, 544, 13.
[36] Koyanagi, G. K.; Caraiman, D.; Blagojevic, V.; Bohme, D. K. J. Phys. Chem. A 2002, 106, 4581.
[37] Yao, C.; Guan, W.; Song, P.; Su, Z. M.; Feng, J. D.; Yan, L. K.; Wu, Z. J. Theor. Chem. Acc. 2007, 117, 115.
[38] Gong, Y.; Zhou, M. F.; Andrews, L. Chem. Rev. 2009, 109, 6765.
[39] Wang, B.; Chen, W. J.; Zhao, B. C.; Zhang, Y. F.; Huang, X. J. Phys. Chem. A 2010, 114, 1964.
[40] Zhai, H. J.; Zhang, X. H.; Chen, W. J.; Huang, X.; Wang, L. S. J. Am. Chem. Soc. 2011, 133, 3085.
[41] Chen, W. J.; Zhai, H. J.; Huang, X.; Wang, L. S. Chem. Phys. Lett. 2011, 512, 49.
[42] Xu, L.; Xia, C. J.; Wang, L. F.; Xie, L.; Wang, B.; Zhang, Y. F.; Huang, X. RSC Adv. 2014, 4, 60270.
[43] Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
[44] Lee, C.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
[45] Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
[46] Andrae, D.; Häußermann, U.; Dolg, M.; Stoll, H.; Preuß, H. Theor. Chim. Acta 1990, 77, 123.
[47] Kuchle, W.; Dolg, M.; Stoll, H.; Preuss, H. Pseudopotentials of the Stuttgart/Dresden Group 1998, revision August11, 1998. .
[48] Martin, J. M. L.; Sundermann, A. J. Chem. Phys. 2000, 114, 3408.
[49] Dunning, Jr. T. H. J. Chem. Phys. 1989, 90, 1007.
[50] Kendall, R. A.; Dunning, Jr. T. H. J. Chem. Phys. 1992, 96, 6796.
[51] Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, 10180.
[52] Purvis, G.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910.
[53] Scuseria, G. E.; Janssen, C. L.; Schaefer Ⅲ, H. F. J. Chem. Phys. 1988, 89, 7382.
[54] Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157, 479.
[55] Watts, J. D.; Gauss, J.; Bartlett, R. J. J. Chem. Phys. 1993, 98, 8718.
[56] Bartlett, R. J.; Musial, M. Rev. Mod. Phys. 2007, 79, 291.
[57] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; 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.; Bakken, V.; 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 03, Revision D.01, Gaussian, Inc., Wallingford, CT, 2004.
[58] Werner, H. J.; Knowles, P. J.; Knizia, G.; Manby, F. R.; Schütz, M.; Celani, P.; Györffy, W.; Kats, D.; Korona, T.; Lindh, R.; Mitrushenkov, A.; Rauhut, G.; Shamasundar, K. R.; Adler, T. B.; Amos, R. D.; Bernhardsson, A.; Berning, A.; Cooper, D. L.; Deegan, M. J. O.; Dobbyn, A. J.; Eckert, F.; Goll, E.; Hampel, C.; Hesselmann, A.; Hetzer, G.; Hrenar, T.; Jansen, G.; Köppl, C.; Liu, Y.; Lloyd, A. W.; Mata, R. A.; May, A. J.; McNicholas, S. J.; Meyer, W.; Mura, M. E.; Nicklaß, A.; O'Neill, D. P.; Palmieri, P.; Peng, D.; Pflüger, K.; Pitzer, R.; Reiher, M.; Shiozaki, T.; Stoll, H.; Stone, A. J.; Tarroni, R.; Thorsteinsson, T.; Wang, M. MOLPRO, Version 2010.1, a package of ab initio programs,.
[59] Humphrey, W.; Dalke, A.; Schulten, K. J. Mol. Graphics 1996, 14, 33.
[60] Kim, J. B.; Weichman, M. L.; Neumark, D. M. J. Am. Chem. Soc. 2014, 136, 7159.
[61] Morse, P. M.; Wilson, S. R.; Girolami, G. S. Inorg. Chem. 1990, 29, 3200.
[62] Che, M.; Tench, A. J. Adv. Catal. 1982, 31, 77.
[63] Che, M.; Tench, A. J. Adv. Catal. 1983, 32, 1.
[64] Wang, L. S.; Wu, H.; Desai, S. R. Phys. Rev. Lett. 1996, 76, 4853.
[65] Wang, L. S.; Wu, H.; Desai, S. R.; Lou, L. Phys. Rev. B 1996, 53, 8028.
[66] Wu, H.; Li, X.; Wang, X. B.; Ding, C. F.; Wang, L. S. J. Chem. Phys. 1998, 109, 449.
[67] Zhai, H. J.; Wang, L. S. J. Chem. Phys. 2002, 117, 7882.
[68] Huang, X.; Zhai, H. J.; Waters, T.; Li, J.; Wang, L. S. Angew. Chem. Int. Ed. 2006, 118, 673.

二核铪氧簇Hf₂O_n^-/0(n=1~6)的电子性质与结构演化的理论研究

Theoretical Study on Electronic Properties and Structural Evolution in Hf₂O_n^-/0 (n=1~6) Clusters

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	李珊, 路俊欣, 刘杰, 蒋绿齐, 易文斌. 氟烷基亚磺酸钠盐电化学合成α-氟烷基酮[J]. 化学学报, 2024, 82(2): 110-114.
[2]	邓沈娜, 彭常春, 牛云宏, 许云, 张云霄, 陈祥, 王红敏, 刘珊珊, 沈晓. 自由基Brook重排调控的α-氟烷基-α-硅基甲醇参与的烯烃双官能团化反应[J]. 化学学报, 2024, 82(2): 119-125.
[3]	陈健强, 朱钢国, 吴劼. 镍催化氮杂环丙烷的开环偶联反应研究[J]. 化学学报, 2024, 82(2): 190-212.
[4]	李雅宁, 王晓艳, 唐勇. 自由基聚合的立体选择性调控^★[J]. 化学学报, 2024, 82(2): 213-225.
[5]	易敬霖, 陈茂. 三氟氯乙烯与甲基异丙烯基醚的光诱导共聚反应^★[J]. 化学学报, 2024, 82(2): 126-131.
[6]	黄广龙, 薛小松. “陈试剂”作为三氟甲基源机理的理论研究[J]. 化学学报, 2024, 82(2): 132-137.
[7]	任妍妍, 李欣, 韩英锋. 基于氮杂环卡宾蓝光有机自由基的合成及其光学性质研究^★[J]. 化学学报, 2023, 81(7): 735-740.
[8]	梁雪峰, 荆剑, 冯昕, 赵勇泽, 唐新员, 何燕, 张立胜, 李慧芳. 共价有机框架COF66/COF366的电子结构: 从单体到二维平面聚合物[J]. 化学学报, 2023, 81(7): 717-724.
[9]	刘坜, 郑刚, 范国强, 杜洪光, 谭嘉靖. 4-酰基/氨基羰基/烷氧羰基取代汉斯酯参与的有机反应研究进展[J]. 化学学报, 2023, 81(6): 657-668.
[10]	杨磊, 葛娇阳, 王访丽, 吴汪洋, 郑宗祥, 曹洪涛, 王洲, 冉雪芹, 解令海. 一种基于芴的大环结构的有效降低内重组能的理论研究[J]. 化学学报, 2023, 81(6): 613-619.
[11]	杨洁, 凌琳, 李玉学, 吕龙. 高氯酸铵热分解机理的密度泛函理论研究[J]. 化学学报, 2023, 81(4): 328-337.
[12]	张少秦, 李美清, 周中军, 曲泽星. 多共振热激活延迟荧光过程的理论研究[J]. 化学学报, 2023, 81(2): 124-130.
[13]	赵亚婷, 刘帆, 汪秋安, 夏吾炯. 可见光促进(氮杂)芳香胺与重氮乙酸乙酯的N-烷基化反应[J]. 化学学报, 2023, 81(2): 111-115.
[14]	王娟, 肖华敏, 谢丁, 郭元茹, 潘清江. 铜掺杂与氮化碳复合氧化锌材料结构和二氧化氮气体传感性质的密度泛函理论计算[J]. 化学学报, 2023, 81(11): 1493-1499.
[15]	陈健强, 朱钢国, 吴劼. 草酸酯类化合物在自由基脱羟基化反应中的研究进展[J]. 化学学报, 2023, 81(11): 1609-1623.