对含重元素体系的接合二分量-标量相对论密度泛函计算方法

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (2): 299.

对含重元素体系的接合二分量-标量相对论密度泛函计算方法

王繁, 黎乐民, 刘文剑

北京大学化学与分子工程学院, 稀土材料化学及应用国家重点实验室, 北京 100871

收稿日期:2003-08-12 出版日期:2004-02-24 发布日期:2004-02-24
通讯作者: 黎乐民(1935年出生),男,教授,博士生导师,中国科学院院士,从事理论化学研究.E-mail;lilm@pku.edu.cn E-mail:lilm@pku.edu.cn
基金资助:
国家自然科学基金(批准号;2033302);教育部博士后科研流动站科学基金资助

A Scheme for Jointed Two Component-scalar Relativistic Density Functional Calculations of Systems Containing Heavy Elements

WANG Fan, LI Le-Min, LIU Wen-Jian

State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Received:2003-08-12 Online:2004-02-24 Published:2004-02-24

摘要/Abstract

摘要： 在相对论密度泛函ZORA方法的基础上,提出一种用于含重元素体系的接合二分量-标量相对论密度泛函计算方法.对于只含少数几个重元素的较大体系,仅对其中旋轨耦合作用强的重元素作二分量相对论计算,而对体系的其余部分则作标量相对论计算,通过对动能矩阵元的近似处理实现两种计算的接合.对一系列含6p区重元素分子进行计算的结果表明,当非重元素是第三周期以前的元素时,此方法与二分量ZO-RA方法的计算结果吻合得很好.当非重元素为第四周期元素时,计算结果有一定偏差,表明在后一种情况下旋轨耦合作用已比较显著,但误差仍在目前近似密度泛函计算的精度范围内.此方法可以有效地节省计算量,而且避免了Dyall方法的缺点.

关键词: 密度泛函计算, ZORA方法, 含重元素体系, 旋轨耦合作用, BDF程序包

Abstract: A scheme for joined two component-scalar relativistic density functional calculations of systems containing a few heavy atoms is proposed based on the relativistic density functional ZORA method with an atomic model potential approximation. The two component-relativistic density functional computation is performed only for a few heavy atoms with strong spin-orbit effects in the system, while the reminder part of the system is treated with the scalar relativistic density functional method, resulting in considerably reduction of computational efforts. The two kinds of computations are joined through a reasonable approximation in the calculation of kinetic energy matrix elements. The calculations for a series of molecules containing 6p block heavy elements are performed by using the proposed scheme and the normal two component-ZORA method. It is found that the results from the two kinds of calculations are in excellent agreement to each other when the lighter atoms belong to the second or third period. If the “non-heavy” atoms belong to the fourth period, the results from the proposed scheme slightly deviate from those obtained by the normal two component-ZORA calculations, showing that the spin-orbit effects have become significant relatively and cannot be neglected in the calculations with a high accuracy required. However, even in that case, the accuracy of the calculated results is still compatible with that of the current approximate density functionals and can satisfied the requirement for ordinary theoretical studies. The proposed scheme can effectively save computation efforts while the defects in Dyall′s method can be avoided.

Key words: Density functional calculations, ZORA method, Systems containing heavy elements, Spin-orbit coupling interaction, BDF program package

中图分类号:

O641

TrendMD:

王繁, 黎乐民, 刘文剑. 对含重元素体系的接合二分量-标量相对论密度泛函计算方法. 高等学校化学学报, 2004, 25(2): 299.

WANG Fan, LI Le-Min, LIU Wen-Jian . A Scheme for Jointed Two Component-scalar Relativistic Density Functional Calculations of Systems Containing Heavy Elements. Chem. J. Chinese Universities, 2004, 25(2): 299.

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