(Ba_(1-x)K_x)BiO_3电子结构与超导电性

用第一原理的ＬＤＦ-ＬＭＴＯ-ＡＳＡ超元胞法，模拟由Ｘ射线吸收谱精细结构测定的ＢａＢｉＯ_３中，Ｂｉ有两种价态Ｂｉ^３＋和Ｂｉ^5＋及与之相应的两种不同键长的Ｂｉ—Ｏ八面体，以及Ｋ掺杂对晶体结构的影响．计算了Ｂａ₄Ｂｉ₄Ｏ₁₂，（Ｂａ_３Ｋ）Ｂｉ₄Ｏ₁₂，（ＢａＫ）Ｂｉ₂Ｏ₆，（ＢａＫ_３）Ｂｉ₄Ｏ₁₂，Ｋ₂Ｂｉ₂Ｏ₆（简记为（４０４），（３１４），（１１２），（１３４），（０２２））五种“样本”的电子结构．结果表明，（４０４）和（３１４）分别为Ｅ_g＝１.６ｅＶ及Ｅ_g＝１.５ｅＶ的半导体，其它“样本”为金属．总能的分析表明（１３４）是不稳定的，故溶解极限为ｘ＝０.５．以“取样”方式按伯努利分布确定任意组分各“样本”的概率，进而计算了（Ｂａ_1-xＫ_x）ＢｉＯ_３电子结构随组分的变化．最后用逾渗模型说明了超导转变温度Ｔ_c在ｘ＝０．２５附近的突变 关键词：

THE ELECTRONIC STRUCTURE AND SUPERCONDUCTIVITY FOR （Ｂａ1-xＫx）ＢｉＯ３

Electronic structure for BKB has been calculated by using LMTO-ASA-Supercell method based on the X-ray absorption fine structure (XAFS) spectroscopy measurements. Measurements show that Bi posseses two valence states Ｂｉ^３＋ and Ｂｉ^5＋ and their Bi—Ｏ bond lengths are diffferent, the difference decreases with the increase of K concentration. Calculations are performed on five samples namely Ｂａ₄Ｂｉ₄Ｏ₁₂（４０４），（Ｂａ_３Ｋ）Ｂｉ₄Ｏ₁₂（３１４），（ＢａＫ）Ｂｉ₂Ｏ₆（１１２），（ＢａＫ_３）Ｂｉ₄Ｏ₁₂（１３４），Ｋ₂Ｂｉ₂Ｏ₆（０２２）.Results from the calculations show that （404）and (314)are semiconductors with gaps of 1.6eV and 1.5eV, respectively. Other samples are metals. Total energy analysis shows that (314) is not stable, so that the extreme value of x is 0.5. The BKB electronic structures at x=0.1 to 0.5 are calculated by combining the probability with sample's Bernoull's distribution. Superconducting transition temperature T_c of BKB is suddenly changed when x approximates to 0.25. The experimental data are close to the prediction values of percolation theory.