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化学进展 2007, Vol. 19 Issue (06): 833-851   后一篇

• 特约稿 •

相对论量子化学新进展*

刘文剑**   

  1. 北京分子科学国家实验室 北京大学化学与分子工程学院 北京 100871
  • 收稿日期:2007-04-23 修回日期:2007-04-24 出版日期:2007-06-24 发布日期:2007-06-24
  • 通讯作者: 刘文剑
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New Advances in Relativistic Quantum Chemistry

Liu Wenjian**   

  1. Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China
  • Received:2007-04-23 Revised:2007-04-24 Online:2007-06-24 Published:2007-06-24
本文详细阐述了相对论量子化学的基本概念和原理，在此基础上评述了相对论量子化学领域的最新进展。指出，不靠数学技巧，而仅凭"用原子（分子片）合成分子"这一思想就可以大大简化分子的相对论计算，使四分量完全相对论和二分量准相对论方法在简洁性、计算精度、计算效率诸方面达到完全一致；作者发展的新一代准相对论方法XQR（exact matrix quasi-relativistic theory）不仅准确、简单，而且是联系相对论Dirac方程和非相对论Schrodinger方程的"无缝桥梁"。这是概念上的一大突破。可以说，化学（和普通物理）中的相对论问题已经得到解决。本文还展望了相对论量子化学未来的发展方向。
关键词： 重元素, 相对论效应, 极小极大变分原理, 动能平衡条件, 相对论密度泛函理论, XQR方法, BDF程序
After detailed discussions on the fundamental concepts and principles of relativistic quantum chemistry the new advances in this field are critically reviewed. It is shown that four- and two-component relativistic electronic structure theories can be made fully equivalent in all the aspects of simplicity, accuracy and efficiency. In particular, this has been achieved in terms solely of physical arguments rather than of mathematical tricks. One of the essential ideas is "from atoms to molecule" which fully employs the spatial locality of relativistic effects as well as the knowledge about the atoms forming the molecule. Another essential ingredient is to formulate quasi-relativistic theory on matrix form rather than on operator form. The resultant exact matrix quasi-relativistic theory (XQR) is far simpler than all existent approaches, whether finite- or infinite-order. In addition, the XQR theory provides a seamless bridge between the Dirac and Schrodinger equations. This is a great breakthrough in concept. It is now justified to claim that relativity in chemistry (and ordinary physics) has been solved！Future perspectives of relativistic quantum chemistry are provided as well.
Key words: heavy elements, relativistic effects, minimax variational principle, kinetic balance condition, relativistic density functional theory, matric quasi-relativistic theory(XQR), BDF program

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相对论量子化学新进展*