• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >The Challenge of the So-Called Electron Configurations of the Transition Metals
【24h】

The Challenge of the So-Called Electron Configurations of the Transition Metals

机译：所谓过渡金属电子构型的挑战

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Quite different meanings are attached by chemists to the words element,atom,orbital,order of orbitals or configurations.This causes conceptual inconsistencies,in particular with respect to the transition-metal elements and their atoms or ions.The different meanings will here be distinguished carefully.They are analyzed on the basis of empirical atomic spectral data and quasi-relativistic density functional calculations.The latter are quite reliable for different average configuration energies of transition-metal atoms.The so-called"configurations of the chemical elements",traditionally displayed in periodic tables,are the dominant configurations of the lowest spin-orbit levels of the free atoms.They are chemically rather irrelevant.In many-electron systems the ns and np AOs are significantly below the more hydrogen-like nd ones.Even(n + l)s is below nd for all light neutral atoms from C onwards,but only up to the first elements of the respective long rows! The most common orbital order in transition-metal atoms is 3p 3d < 4s etc.The chemically relevant configuration in group g is always d~g instead of d~(g-2)s~2.Conceptually clear reasoning eliminates apparent textbook inconsistencies between simple quantum-chemical models and the empirical facts.The empirically and theoretically well-founded Rydberg(n-delta_l)rule is to be preferred instead of the historical Ma-delung(n + l)rule with its large number of exceptions.
机译：化学家对元素，原子，轨道，轨道或构型的顺序赋予了完全不同的含义。这引起了概念上的不一致，特别是在过渡金属元素及其原子或离子方面。这里将区分不同的含义。在经验原子光谱数据和准相对论密度泛函计算的基础上对它们进行了仔细分析。后者对于过渡金属原子的不同平均构型能是相当可靠的。传统上，所谓的“化学元素构型”周期表中显示的是自由原子的最低自旋轨道能级的主要构型，它们在化学上是无关紧要的。在多电子系统中，ns和np AO明显低于类似氢的nd和AO。对于从C开始的所有轻中性原子，n + l）s都在nd之下，但仅直到相应长行的第一个元素为止！过渡金属原子中最常见的轨道顺序是3p 3d <4s等.g组中化学相关的构型始终是d〜g而不是d〜（g-2）s〜2。从概念上讲清楚的推理消除了明显的教科书简单的量子化学模型与经验事实之间的矛盾。具有丰富经验和理论依据的Rydberg（n-delta_l）规则应优先于历史Ma-delung（n + l）规则，但有很多例外。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号