Citation: WEI Mei-Ju, JIA De-Qiang, CHEN Fei-Wu. Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂[J]. Acta Physico-Chimica Sinica, ;2013, 29(07): 1441-1452. doi: 10.3866/PKU.WHXB201304221 shu

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂

1.
School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China

Received Date: 21 January 2013
Available Online: 22 April 2013
Fund Project: 国家自然科学基金(21173020) (21173020)中央高校基本科研业务费专项资金(FRF-TP-12-114A, FRF-BR-11-026B)资助项目 (FRF-TP-12-114A, FRF-BR-11-026B)

The geometries of the ground and excited states of titanium dioxide, ¹A₁, ¹B₂, ³B₂, ¹B₁, ³B₁, ¹A₂ and ³A₂, have been optimized using Møller-Plesset second-order perturbation theory, density functional theory B3LYP, and time-dependent density functional theory TD-B3LYP methods. ¹A₁, ¹B₂, ³B₂, ¹B₁ and ³B₁ have bent structures, while ¹A₂and ³A₂ have symmetrical linear structures. The bond angles of ¹B₂, ³B₂, ¹B₁ and ³B₁ correlate directly with the magnitudes of the corresponding bond dipole moments. Vertical and adiabatic excitation energies have been computed with complete active space self-consistent field (CASSCF) CASSCF(6,6), CASSCF(8,8), multi-reference configuration interaction (MRCI), and TD-B3LYP. For ¹B₂、³B₂and ¹B₁, the excitation energies calculated with MRCI/CASSCF(6,6) are much closer to the experimental values than the results calculated using other methods. For excited states ³B₁, ¹A₂ and ³A₂, excitation energies calculated with CASSCF(6,6), CASSCF(8,8), MRCI, and TD-B3LYP are almost consistent with theoretical results available in the literature. Dipole moments of the ground and excited states have been computed with B3LYP and TD-B3LYP. The calculated dipole moments of ¹A₁ and ¹B₂ agree well with experimental data. The atomic charges of TiO₂ in ground and excited states have been calculated with the atomic dipole moment corrected Hirshfeld population method. This calculation revealed that changes of dipole moments from the ground state to the excited states are related to electron transfer from the oxygen atom to the titanium atom. During the above calculations, the influences of the basis sets cc-pVDZ, cc-pVTZ, and cc-pVQZ were also investigated.
- TiO₂,
- Geometrical structure,
- Vertical excitation energy,
- Adiabatic excitation energy,
- Dipole moment
1. [1]
  
  (1) Fujishima, A; Honda, K. Nature 1972, 37, 238.
2. [2]
  (2) Chen, X.; Mao, S. S. Chem. Rev. 2007, 107, 2891. doi: 10.1021/cr0500535
3. [3]
  (3) Kubacka, A.; Fernández-García, M.; Colón, G. Chem. Rev.2012, 112, 1555. doi: 10.1021/cr100454n
4. [4]
  (4) Youngblood,W. J.; Lee, S. H. A.; Maeda, K.; Mallouk, T. E.Accounts Chem. Res. 2009, 42 (12), 1966. doi: 10.1021/ar9002398
5. [5]
  (5) Qian, D. F.; Zhang, Q. H.;Wan, J.; Li, Y. G.;Wang, H. Z. Acta Phys. -Chim. Sin. 2010, 26 (10), 2745. [钱迪峰, 张青红,万钧, 李耀刚, 王宏志. 物理化学学报, 2010, 26 (10), 2745.]doi: 10.3866/PKU.WHXB20100948
6. [6]
  (6) Chen, H.; Nanayakkara, C. E.; Grassian, V. H. Chem. Rev. 2012,112, 5919. doi: 10.1021/cr3002092
7. [7]
  (7) Shen,W. R.; Zhao,W. K.; He, F.; Fang, Y. L. Progress in Chemistry 1998, 10 (4), 349. [沈伟韧, 赵文宽, 贺飞, 方佑龄. 化学进展, 1998, 10 (4), 349.]
8. [8]
  (8) Thompson, T. L.; Yates, J. T. Chem. Rev. 2006, 106, 4428. doi: 10.1021/cr050172k
9. [9]
  (9) Yan, B. X.; Luo, S. Y.; Shen, J. Acta Phys. -Chim. Sin. 2012, 28 (2), 381. [颜秉熙, 罗胜耘, 沈杰. 物理化学学报, 2012, 28 (2), 381.] doi: 10.3866/PKU.WHXB201112123
10. [10]
  (10) Grein, F. J. Chem. Phys. 2007, 126, 034313. doi: 10.1063/1.2429062
11. [11]
  (11) Taylor, D. J.; Paterson, M. J. J. Chem. Phys. 2010, 133, 204302.doi: 10.1063/1.3515477
12. [12]
  (12) Kaufman, M.; Muenter, J.; Klemperer,W. J. Chem. Phys. 1965,47, 3365.
13. [13]
  (13) McIntyre, N. S.; Thompson, K. R.;Weltner,W. J. Phys. Chem.1971, 75, 3243.
14. [14]
  (14) Chertihin, G. V.; Andrews, L. J. Phys. Chem. 1995, 99, 6356.doi: 10.1021/j100017a015
15. [15]
  (15) Brünken, S.; Müller, H. S. P.; Menten, K. M.; McCarthy, M. C.;Thaddeus, P. A. Astrophys. J. 2008, 676, 1367. doi: 10.1086/523316
16. [16]
  (16) Wang, H.; Steimle, T. C.; Apetrei, C.; Maier, J. P. Phys. Chem. Chem. Phys. 2009, 11, 2649. doi: 10.1039/b821849h
17. [17]
  (17) Zhuang, X.; Le, A.; Steimle, T. C.; Nagarajan, R.; Gupta, V.;Maier, J. P. Phys. Chem. Chem. Phys. 2010, 12, 15018. doi: 10.1039/c0cp00861c
18. [18]
  (18) Wu, H.;Wang, L. S. J. Chem. Phys. 1997, 107, 8221. doi: 10.1063/1.475026
19. [19]
  (19) Garkusha, I.; Nagy, A.; Guennoun, Z.; Maier, J. P. Chem. Phys.2008, 353, 115. doi: 10.1016/j.chemphys.2008.08.003
20. [20]
  (20) Ramana, M. V.; Phillips, D. H. J. Chem. Phys. 1988, 88, 2637.doi: 10.1063/1.454716
21. [21]
  (21) Hagfeldt, A.; Bergström, R.; Siegbahn, H. O. G.; Lunell, S.J. Phys. Chem. 1993, 97, 12725. doi: 10.1021/j100151a016
22. [22]
  (22) Bergström, R.; Lunell, S.; Eriksson, L. A. Int. J. Quantum Chem. 1996, 59, 427.
23. [23]
  (23) Walsh, M. B.; King, R.; Schaefer, H. F. J. Chem. Phys. 1999,110, 5224. doi: 10.1063/1.478418
24. [24]
  (24) Albaret, T.; Finocchi, F.; Noguera, C. J. Chem. Phys. 2000, 113,2238. doi: 10.1063/1.482038
25. [25]
  (25) Qu, Z.W.; Kroes, G. J. J. Phys. Chem. B 2006, 110, 8998. doi: 10.1021/jp056607p
26. [26]
  (26) Li, S.; Dixon, D. A. J. Phys. Chem. A 2008, 112, 6646. doi: 10.1021/jp800170q
27. [27]
  (27) Liu, Y.; Yuan, Y.;Wang, Z.; Deng, K.; Xiao, C.; Li, Q. J. Chem. Phys. 2009, 130, 174308. doi: 10.1063/1.3126776
28. [28]
  (28) Woon, D. E.; Dunning, T. H. J. Chem. Phys. 1993, 98, 1358.doi: 10.1063/1.464303
29. [29]
  (29) Kendall, R. A.; Dunning, T. H.; Harrison, R. J. J. Chem. Phys.1992, 96, 6796. doi: 10.1063/1.462569
30. [30]
  (30) Dunning, T. H. J. Chem. Phys. 1989, 90, 1007. doi: 10.1063/1.456153
31. [31]
  (31) Moller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618. doi: 10.1103/PhysRev.46.618
32. [32]
  (32) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
33. [33]
  (33) Lee, C.; Yang,W.; Parr, G. R. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
34. [34]
  (34) Zhao, G. J.; Han, K. L. Accounts Chem. Res. 2012, 45, 404. doi: 10.1021/ar200135h
35. [35]
  (35) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys.1998, 109, 8218. doi: 10.1063/1.477483
36. [36]
  (36) Bauernschmitt, R.; Ahlrichs, R. Chem. Phys. Lett. 1996, 256,454. doi: 10.1016/0009-2614(96)00440-X
37. [37]
  (37) Casida, M. E.; Jamorski, C.; Casida, K. C.; Salahub, D. R.J. Chem. Phys. 1998, 108, 4439. doi: 10.1063/1.475855
38. [38]
  (38) Foresman, J. B.; Head- rdon, M.; Pople, J. A.; Frisch, M. J.J. Phys. Chem.1992, 96, 135. doi: 10.1021/j100180a030
39. [39]
  (39) Hegarty, D.; Robb, M. A. Mol. Phys. 1979, 38, 1795. doi: 10.1080/00268977900102871
40. [40]
  (40) Yamamoto, N.; Vreven, T.; Robb, M. A.; Frisch, M. J.; Schlegel,H. B. Chem. Phys. Lett. 1996, 250, 373. doi: 10.1016/0009-2614(96)00027-9M
41. [41]
  (41) Werner, H. J.; Knowles, P. J. J. Chem. Phys. 1988, 89, 5803.doi: 10.1063/1.455556
42. [42]
  (42) Knowles, P. J.;Werner, H. J. Chem. Phys. Lett. 1988, 145, 514.doi: 10.1016/0009-2614(88)87412-8
43. [43]
  (43) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 03 W, Revision D.01; Gaussian Inc.: Pittsburgh, PA, 2003.
44. [44]
  (44) Wemer, H. J.; Knowles, P. J.; Lindh, R.; MAnby, F. R.; Schütz,M. et al. Molpro, 2009.1; a Package of ab initio Programs. seehttp://www.molpro.net.
45. [45]
  (45) Lu, T.; Chen, F.W. J. Thero. Comput. Chem. 2012, 11 (1), 163.doi: 10.1142/S0219633612500113
46. [46]
  (46) Lu, T.; Chen, F.W. Acta Phys. -Chim. Sin. 2012, 28 (1), 1.[卢天, 陈飞武. 物理化学学报, 2012, 28 (1), 1.] doi: 10.1142/10.3866/PKU.WHXB2012281
47. [47]
  (47) Lu, T.; Chen, F.W. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
48. [48]
  (48) http://Multiwfn.codeplex.com.
1. [1]
  Shengjuan Huo , Xiaoyan Zhang , Xiangheng Li , Xiangning Li , Tianfang Chen , Yuting Shen . Unveiling the Marvels of Titanium: Popularizing Multifunctional Colored Titanium Product Films. University Chemistry, 2024, 39(5): 184-192. doi: 10.3866/PKU.DXHX202310127
2. [2]
  Ruiqing LIU , Wenxiu LIU , Kun XIE , Yiran LIU , Hui CHENG , Xiaoyu WANG , Chenxu TIAN , Xiujing LIN , Xiaomiao FENG . Three-dimensional porous titanium nitride as a highly efficient sulfur host. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 867-876. doi: 10.11862/CJIC.20230441
3. [3]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
4. [4]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
5. [5]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
6. [6]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
7. [7]
  Yixuan Gao , Lingxing Zan , Wenlin Zhang , Qingbo Wei . Comprehensive Innovation Experiment: Preparation and Characterization of Carbon-based Perovskite Solar Cells. University Chemistry, 2024, 39(4): 178-183. doi: 10.3866/PKU.DXHX202311091
8. [8]
  Yunxin Xu , Wenbo Zhang , Jing Yan , Wangchang Geng , Yi Yan . A Fascinating Saga of “Energetic Materials”. University Chemistry, 2024, 39(9): 266-272. doi: 10.3866/PKU.DXHX202307008
9. [9]
  Zeyuan WANG , Songzhi ZHENG , Hao LI , Jingbo WENG , Wei WANG , Yang WANG , Weihai SUN . Effect of I₂ interface modification engineering on the performance of all-inorganic CsPbBr₃ perovskite solar cells. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1290-1300. doi: 10.11862/CJIC.20240021
10. [10]
  Jizhou Liu , Chenbin Ai , Chenrui Hu , Bei Cheng , Jianjun Zhang . 六氯锡酸铵促进钙钛矿太阳能电池界面电子转移及其飞秒瞬态吸收光谱研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2402006-. doi: 10.3866/PKU.WHXB202402006
11. [11]
  Xiao Liu , Guangzhong Cao , Mingli Gao , Hong Wu , Hongyan Feng , Chenxiao Jiang , Tongwen Xu . Seawater Salinity Gradient Energy’s Job Application in the Field of Membranes. University Chemistry, 2024, 39(9): 279-282. doi: 10.3866/PKU.DXHX202306043
12. [12]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . Kinetic Resolution Enabled by Photoexcited Chiral Copper Complex-Mediated Alkene E→Z Isomerization: A Comprehensive Chemistry Experiment for Undergraduate Students. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
13. [13]
  Junli Liu . Practice and Exploration of Research-Oriented Classroom Teaching in the Integration of Science and Education: a Case Study on the Synthesis of Sub-Nanometer Metal Oxide Materials and Their Application in Battery Energy Storage. University Chemistry, 2024, 39(10): 249-254. doi: 10.12461/PKU.DXHX202404023
14. [14]
  Xinxin JING , Weiduo WANG , Hesu MO , Peng TAN , Zhigang CHEN , Zhengying WU , Linbing SUN . Research progress on photothermal materials and their application in solar desalination. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1033-1064. doi: 10.11862/CJIC.20230371
15. [15]
  Yuanyin Cui , Jinfeng Zhang , Hailiang Chu , Lixian Sun , Kai Dai . Rational Design of Bismuth Based Photocatalysts for Solar Energy Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2405016-. doi: 10.3866/PKU.WHXB202405016
16. [16]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, 2024, 39(5): 98-107. doi: 10.3866/PKU.DXHX202310026
17. [17]
  Simin Fang , Hong Wu , Wei Liu , Wei Wei , Hongyan Feng , Wan Li . Construction and Application of Teaching Resources for Inorganic and Analytical Chemistry Experimental Course in the Context of Digital Empowerment. University Chemistry, 2024, 39(10): 156-163. doi: 10.3866/PKU.DXHX202402053
18. [18]
  Yipeng Zhou , Chenxin Ran , Zhongbin Wu . Metacognitive Enhancement in Diversifying Ideological and Political Education within Graduate Course: A Case Study on “Solar Cell Performance Enhancement Technology”. University Chemistry, 2024, 39(6): 151-159. doi: 10.3866/PKU.DXHX202312096
19. [19]
  Yongming Zhu , Huili Hu , Yuanchun Yu , Xudong Li , Peng Gao . Construction and Practice on New Form Stereoscopic Textbook of Electrochemistry for Energy Storage Science and Engineering: Taking Basic Course of Electrochemistry as an Example. University Chemistry, 2024, 39(8): 44-47. doi: 10.3866/PKU.DXHX202312086
20. [20]
  Honglian Liang , Xiaozhe Kuang , Fuping Wang , Yu Chen . Exploration and Practice of Integrating Ideological and Political Education into Physical Chemistry: a Case on Surface Tension and Gibbs Free Energy. University Chemistry, 2024, 39(10): 433-440. doi: 10.12461/PKU.DXHX202405073

Get Citation

PDF

XML

Metrics

PDF Downloads(754)
Abstract views(986)
HTML views(62)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO2

Metrics

通讯作者: 陈斌, bchen63@163.com

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂