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对O原子采用6-311++G*基组，Zr原子采用aug-cc-pVTZ-PP基组，利用密度泛函（B3P86）方法优化得到了ZrO2分子的稳定构型，并研究了不同外电场（0–0.025 a.u.）作用下ZrO2 基态分子键长、能量、电荷分布、偶极矩和能级的变化规律. 在优化构型的基础上，利用含时密度泛函（TD-B3P86）方法研究了ZrO2分子在外电场作用下前6个激发态的激发能、跃迁波长和振子强度的激发特性. 研究结果表明：随着电场强度的增大，Zr–2O的键长增大，而Zr–3O的键长均匀减少，总能量降低，偶极矩增大；最高占据轨道能量基本保持不变，最低未占据轨道和能隙均减小. 电场的增大使得激发能减小，各个激发态跃迁波长均发生不同程度的红移现象，因而，利用外电场可以控制ZrO2的发光光谱范围在可见-红外区域扩展.In order to study the influence of external electric field on ZrO2, molecular structure of ZrO2 ground state is optimized by density functional theory (B3P86) method with 6-311++G* basis sets for O atom and aug-cc-pVTZ-PP for Zr atom. The effects of electric field ranging from 0 to 0.025 a.u. are investigated on bond length, total energy, charge distribution, dipole moment, HOMO (the highest occupied molecular orbital) energy level, LUMO (the lowest unoccupied molecular orbital) energy level and energy gap. The excitation energies, transition wavelengths and oscillator strengths under the same intense external electric fields are calculated by the time dependent density functional theory (TD-B3P86) method. The result shows that the bond length of Zr-2O and total energy increase with external field increasing, but the bond lengths of Zr-3O, LUMOs and energy gaps decrease, and HOMOs almost keep the same. The excitation energies decrease and the transition wavelengths of the six excited states are red shifted toward longer wavelength as the applied electric field increases. Therefore the spectral region of zirconiumdioxide molecule can be expanded in visible-infrared region by the use of external electric fields.
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Keywords:
- ZrO2 /
- electric field /
- ground states /
- excited properties
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[1] Rao C N, Raveau B 1998 Transition Metal Oxides (New York: Wiley)
[2] Gates B C 1995 Chem. Rev. 95 511
[3] Clair T P S, Goodman D W 2000 Top. Catal. 13 5
[4] Wallace W T, Min B K, Goodman D W 2005 Top. Catal. 34 17
[5] Harrison H D, McLamednt E, Subbarao E C 1962 Electrochem. Soc. 110 23
[6] Liu H Q, Wang L L, Qin W P 2004 Acta Phys. Sin. 53 282 (in Chinese) [刘晃清, 王玲玲, 秦伟平 2004 53 282]
[7] Liu J X, L S C, Li X M 2004 J. Chin. Rare Earth Soc. 22 867 (in Chinese) [刘金霞, 吕树臣, 李秀明 2004 中国稀土学报 22 867]
[8] Hyppänen I, Hölsä J, Kankare J, Lastusaari M, Pihlgren L 2007 J. Nano. Mater. 2007 16391
[9] French R H, Glass S J, Ohuchi F S 1994 Phys. Rev. B 49 5133
[10] Ghosh P, Priolkar K R, Patra A 2007 J. Phys. Chem. C 111 571
[11] Jeon S, Braun P V 2003 Chem. Mater. 15 1256
[12] Savoini B, Muñoz Santiuste J E, Gonzalez R 1997 Phys. Rev. B 56 5856
[13] Chen S G, Yu M Y, Hu B G, Wang X, Liu Y C, Yu S Q, Zhang W W, Yin Y S 2007 J. Chin. Ceram. Soc. 35 46 (in Chinese) [陈守刚, 于美燕, 胡保革, 王昕, 刘英才, 于帅琴, 张伟伟, 尹衍升 2007 硅酸盐学报 35 46]
[14] Zhao G F, Xiang B, Shen X F, Sun J M, Bai Y Z, Wang Y X 2011 Acta Phys. Chim. Sin. 27 1095
[15] Foltin M, Stueber G J, Bernstein E R 2011 J. Chem. Phys. 114 8971
[16] Ma M Z, Zhu Z H, Chen X J, Xu G L, Zhang Y B, Mao H P, Shen X H 2005 Chin. Phys. B 14 1101
[17] Xu G L, Liu X F, Xie H X, Zhang X Z, Liu Y F 2010 Chin. Phys. B 19 113101
[18] Hu Z G, Tian Y T, Li X J 2013 Chin. Phys. Lett. 30 087801
[19] Xu G L, Xie H X, Yuan W, Zhang X Z, Liu Y F 2012 Acta Phys. Sin. 61 043104 (in Chinese) [徐国亮, 谢会香, 袁伟, 张现周, 刘玉芳 2012 61 043104]
[20] Perdew P 1986 J. Phys. Rev. B 33 8822
[21] Cooper G, Olney T N, Brion C E 1995 Chem. Phys. 194 175
[22] Hennico G, Delhalleet 1988 J. Chem. Phys. Lett. 152 207
[23] Grozema F C, Telesca R, Joukman H T, Siebbeles L D A, Snijders J G 2001 J. Chem. Phys. 115 10014
[24] Kjeellberg P, He Z, Pullerrits T 2003 J. Phys. Chem. B 107 13737
[25] Zhu Z H, Fu Y B, Gao T, Chen Y L, Chen X J 2003 Chin. Atom Mol. Phys. 20 169 (in Chinese) [朱正和, 傅依备, 高涛, 陈银亮, 陈晓军 2003 原子与分子 20 169]
[26] Chaudhuri R K, Mudholkar A, Freedet K F 1997 J. Chem. Phys. 106 9252
[27] Zeng J Y 1998 Introduction to Quantum Mechanics (Beijing: Peking University Press) pp 339–341 (in Chinese) [曾谨言 1998 量子力学导论 (北京: 北京大学出版社) 第339–341页]
[28] Woon D E, Dunning T H 1993 J. Chem. Phys. 98 1358
[29] Brugh D J, Suenram R D 1999 J. Chem. Phys. 111 3526
[30] Xu G L, Xiao X H, Liu Y F, Sun J F, Zhu Z H 2007 Acta Phys. Chem. Sin. 23 746 (in Chinese) [徐国良, 肖晓红, 刘玉芳, 孙金峰, 朱正和 2007 物理化学学报 23 746]
[31] Huang D H, Wang F H, Wang M J, Jiang G 2013 Acta Phys. Sin. 62 013104 (in Chinese) [黄多辉, 王藩侯, 王明杰, 蒋刚 2013 62 013104]
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