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

Abstract

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

CLC Number:

O641

TrendMD:

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

References

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