物理化学学报 >> 1990, Vol. 6 >> Issue (05): 580 -588 .doi: 10.3866/PKU.WHXB19900513

研究论文 上一篇    下一篇

Eu3+与Tb3+离子在LnOX系列基质中的配位场微扰能级及其光谱解析

杨频; 李思殿; 王越奎   

  1. 山西大学分子科学研究所,太原;山西运城高等专科学校化学系,运城
  • 收稿日期:1988-12-05 修回日期:1990-04-26 发布日期:1990-10-15
  • 通讯作者: 杨频

Coordination Field Analysis of the Fluorescence Spectra of Eu3+ and Tb3+ Doped in LnOX Matrixes

Yang Pin; Li Si-Dian; Wang Yue-Kui   

  1. Institute of Molecular Science, Shanxi University, Taiyuan; Department of Chemistry, Yuncheng Teachers College, Yuncheng
  • Received:1988-12-05 Revised:1990-04-26 Published:1990-10-15
  • Contact: Yang Pin

摘要: 基于DSCPCF模型, 本文给出LaOX: Eu~3(+)(X~-=Cl~-, Br~-, I~-)和Ln0Cl:Tb~(3+)(Ln~(3+)=La~(3+), Gd~(3+), Y~(3+))系列磷光体的配位场微扰能级, 并对其液氮及液氦温度下的荧光光谱进行了理论归属. 结果表明: (1)DSCPCF微扰能级与实测光谱较好吻合; (2)随着基质阴离子(Cl~-→Br~-→I~-)或阳离子(Y~(3+)→Gd~(3+)→La~(3+))离子半径增大,电负性降低, 晶场参数B_m~k呈增大趋势; (3)配位场微扰导致的电子云膨胀效应与DSCPCF模型的特征参数——配体有效核电荷Z_j~*及键电荷qi的变化趋势相一致; (4)与PCF模型相比, DSCPCF模型使B_m~k的计算结果得到明显改善。

Abstract: Based on Double Sphere Coordination Point Charge Field (DSCPCF) model, the coordination field perturbation energy levels of Eu~(3+) and Tb~(3+) ions doped in LnOX matrixes (Ln~(3+)= La~(3+), Gd~(3+), Y~(3+); X~- = Cl~-, Br~-, I~-) were calculated and the corresponding spectra at liquid nitrogen and liquid helium temperature were assigned. The result shows that 1) the DSCPCF perturbation energy levels agree well with the spectra observed, 2) the coordination field parameters B_m~k show an increasing trend with the increasing of the ionic radius and the electronegativity of both Ln~(3+) and X~- host ions, 3) the Nephelauxetic effect on RE ions and the orbital overlap between RE ion and its ligands are partly revealed by their characteristic parameters--the effective nuclear charge Z_j~* and the bond charge q_j in DSCPCF model, and 4) by comparison with Point Charge Field (PCF) model, B_m~2 in DSCPCF model decrease slightly, while B_m~4 especially B_m~6 increase greatly. This correction may overcome the shortcoming of PCF model in certain degree.