Citation: WANG Fang-Fang, CAO Zhan-Min, CHEN Jun, XING Xian-Ran. Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations[J]. Acta Physico-Chimica Sinica, ;2014, 30(8): 1432-1436. doi: 10.3866/PKU.WHXB201405281 shu

Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations

1.
1. Department of Physical Chemistry, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China;
2. Department of Nonferrous Metallurgy, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China

Received Date: 17 March 2014
Available Online: 28 May 2014
Fund Project:

Recent experimental results have indicated that the negative thermal expansion is a common phenomenon in PbTiO₃-based materials, and that this expansion is affected by various substitutions. Interestingly, Cd substitution in PbTiO₃ has a unique effect compared with other A-site substitutions, in that it enhances negative thermal expansion. Therefore, studying A-site substitution in PbTiO₃, the role of which still remains unclear, would provide a deeper understanding of the nature of the negative thermal expansion of PbTiO₃-based materials. Herein we report the results of structural calculations, densities of states and the minimumelectron densities of Pb_1-xSr_xTiO₃, Pb_1-xBa_xTiO₃, and Pb_1-xCd_xTiO₃ supercells on the basis of chemical bond first-principles calculations. The results demonstrate that the hybridization between Cd―O orbitals is more pronounced than that between Pb―O orbitals, while the bonding between Ba/Sr and O is almost ionic in nature. Cd substitution was found to have an unusual effect in terms of enhancing the average bulk coefficient of thermal expansion in PbTiO₃. In contrast, Ba and Sr substitutions reduce the coefficient. Thus, the covalency in the bonding between the A- site and O in PbTiO₃- based materials is responsible for the enhanced negative thermal expansion.
- Density function theory,
- Negative thermal expansion,
- PbTiO₃,
- Density of states,
- Structure calculation
1. [1]
  
  (1) Xing, X. R.; Deng, J. X.; Chen, J.; Liu, G. R. Rare Met. 2003, 22, 294.
2. [2]
  (2) Chen, J.; Nittala, K.; Forrester, J. S.; Jones, J. L.; Deng, J.; Yu, R.; Xing, X. J. Am. Chem. Soc. 2011, 133 (29), 11114. doi: 10.1021/ja2046292
3. [3]
  (3) Chandra, A.; Pandeya, D.; Mathews, M. D.; Tyagi, A. K. J. Mater. Res. 2005, 20, 350. doi: 10.1557/JMR.2005.0062
4. [4]
  (4) Evans, J. S. O. Dalton Trans. 1999, 19, 3317.
5. [5]
  (5) Mohn, P. Nature 1999, 400, 18. doi: 10.1038/21778
6. [6]
  (6) Zheng, X. G.; Kubozono, H.; Yamada, H.; Kato, K.; Ishiwata, Y.; Xu, C. N. Nat. Nanotechnol. 2008, 3, 724. doi: 10.1038/nnano.2008.309
7. [7]
  (7) Korcök, J. L.; Katz, M. J.; Leznoff, D. B. J. Am. Chem. Soc. 2009, 131, 4866. doi: 10.1021/ja809631r
8. [8]
  (8) Zwanziger, J. W. Phys. Rev. B 2007, 76, 052102.
9. [9]
  (9) Greve, B. K.; Martin, K. L.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.;Wilkinson, A. P. J. Am. Chem. Soc. 2010, 132, 15496. doi: 10.1021/ja106711v
10. [10]
  (10) odwin, A. L.; Calleja, M.; Conterio, M. J.; Dove, M. T.; Evans, J. S. O.; Keen, D. A.; Peters, L.; Tucker, M. G. Science 2008, 319, 794. doi: 10.1126/science.1151442
11. [11]
  (11) Biernacki, S.; SchefBer, M. Phys. Rev. Lett. 1989, 63, 290. doi: 10.1103/PhysRevLett.63.290
12. [12]
  (12) Azuma, M.; Chen, W. T.; Seki, H.; Czapski, M.; Olga, S.; Oka, K.; Mizumaki, M.; Watanuki, T.; Ishimatsu, N.; Kawamura, N.; Ishiwata, S.; Tucker, M. G.; Shimakawa, Y.; Attfield, J. P. Nat. Commun. 2011, 2, 347. doi: 10.1038/ncomms1361
13. [13]
  (13) Pryde, A. K. A.; Hammonds, K. D.; Dove, M. T.; Heine, V.; Gale, J. D.; Warren, M. C. Phase Trans. 1997, 61, 141. doi: 10.1080/01411599708223734
14. [14]
  (14) Chen, J.; Hu, P. H.; Sun, X. Y.; Sun, C.; Xing, X. R. Appl. Phys. Lett. 2007, 91, 171907. doi: 10.1063/1.2794742
15. [15]
  (15) Chen, J.; Xing, X. R.; Sun, C.; Hu, P. H.; Yu, R. B.; Wang, X. W.; Li, L. H. J. Am. Chem. Soc. 2008, 130, 1144. doi: 10.1021/ja7100278
16. [16]
  (16) Chen, J.; Xing, X. R.; Yu, R. B.; Liu, G. R. Appl. Phys. Lett. 2005, 87, 231915. doi: 10.1063/1.2140486
17. [17]
  (17) Wang, F. F.; Xie, Y.; Chen, J.; Fu, H. G.; Xing, X. R. Phys. Chem. Chem. Phys. 2014, 16, 5237. doi: 10.1039/c3cp53197j
18. [18]
  (18) Cheng, H. P.; Chen, G. H.; Qin, R.; Dan, J. K.; Huang, Z. M.; Peng, H.; Chen, T. N., Lei, J. B. Acta Phys. -Chim. Sin. 2014, 30, 281. [程和平,陈光华,覃睿,但加坤,黄智蒙,彭辉,陈图南,雷江波.物理化学学报, 2014, 30, 281.] doi: 10.3866/PKU.WHXB201312171
19. [19]
  (19) Cohen, R. E.; Krakauer, H. Ferroelectrics 1992, 136, 65. doi: 10.1080/00150199208016067
20. [20]
  (20) García, A.; Vanderbilt, D. Phys. Rev. B 1996, 54, 3817. doi: 10.1103/PhysRevB.54.3817
21. [21]
  (21) Cohen, R. E.; Sághi-Szabó, G. Phys. Rev. Lett. 1998, 80, 4321. doi: 10.1103/PhysRevLett.80.4321
22. [22]
  (22) Cockayne, E.; Burton, B. Phys. Rev. B 2004, 69, 144116. doi: 10.1103/PhysRevB.69.144116
23. [23]
  (23) Cohen, R. E. Nature 1992, 358, 136. doi: 10.1038/358136a0
24. [24]
  (24) Grinberg, I.; Rappe, A. M. Phase Trans. 2007, 80, 351. doi: 10.1080/01411590701228505
25. [25]
  (25) Yashima, M.; Omoto, K.; Chen, J.; Kato, H.; Xing, X. R. Chem. Mater. 2011, 23, 3135. doi: 10.1021/cm201184y
26. [26]
  (26) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758.
27. [27]
  (27) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865
28. [28]
  (28) Suárez-Sandoval, D. Y.; Davies, P. K. Appl. Phys. Lett. 2003, 82, 3215. doi: 10.1063/1.1573362
29. [29]
  (29) Kuroiwa, Y.; Aoyagi, S.; Sawada, A.; Harada, J.; Nishibori, E.; Takata, M.; Sakata, M. Phys. Rev. Lett. 2001, 87, 217601. doi: 10.1103/PhysRevLett.87.217601
30. [30]
  (30) Piskunov, S.; Heifets, E.; Eglitis, R. I.; Borstel, G. Comput. Mater. Sci. 2004, 29, 165. doi: 10.1016/j.commatsci.2003.08.036
31. [31]
  (31) Xing, X. R.; Deng, J. X.; Zhu, Z. Q.; Liu, G. R. J. Alloy. Compd. 2003, 353, 1. doi: 10.1016/S0925-8388(02)01178-7
32. [32]
  (32) Xing, X. R.; Chen, J.; Deng, J. X.; Liu, G. R. J. Alloy. Compd. 2003, 360, 286. doi: 10.1016/S0925-8388(03)00345-1
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
3. [3]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
4. [4]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
5. [5]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
8. [8]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
9. [9]
  Yanhui XUE , Shaofei CHAO , Man XU , Qiong WU , Fufa WU , Sufyan Javed Muhammad . Construction of high energy density hexagonal hole MXene aqueous supercapacitor by vacancy defect control strategy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1640-1652. doi: 10.11862/CJIC.20240183
10. [10]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . 前驱体机械压实制备高密度活性炭及其致密电容储能性能. Acta Physico-Chimica Sinica, 2025, 41(3): 2406009-. doi: 10.3866/PKU.WHXB202406009
11. [11]
  Haiping Wang . A Streamlined Method for Drawing Lewis Structures Using the Valence State of Outer Atoms. University Chemistry, 2024, 39(8): 383-388. doi: 10.12461/PKU.DXHX202401073
12. [12]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
13. [13]
  Hua Hou , Baoshan Wang . Course Ideology and Politics Education in Theoretical and Computational Chemistry. University Chemistry, 2024, 39(2): 307-313. doi: 10.3866/PKU.DXHX202309045
14. [14]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
15. [15]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
16. [16]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
17. [17]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
18. [18]
  Hui Li , Jia Nie , Zhongyuan Lü , Hujun Qian , Youliang Zhu , Fuquan Bai , Zexing Qu , Ronglin Zhong . Developing a Lecture Mode for Theoretical and Computational Chemistry Curriculum under the “Modernization of Chinese Education” Initiative. University Chemistry, 2025, 40(3): 1-9. doi: 10.3866/PKU.DXHX202402007
19. [19]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
20. [20]
  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

Get Citation

PDF

XML

Metrics

PDF Downloads(687)
Abstract views(758)
HTML views(7)

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

Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO3 fromFirst-Principles Calculations

Metrics

通讯作者: 陈斌, bchen63@163.com

Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations