Generalized relativistic effective core potential: Theoretical grounds
Generalized relativistic effective core potential: Theoretical grounds
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广义相对论有效核心势：理论基础
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
N. Mosyagin
中科院分区：
文献类型：
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作者：
A. Titov;N. Mosyagin
从理论和计算两方面对广义相对论有效实势方法进行了分析。将冻结核近似中的汉密尔顿量与包含GRECP算子的汉密尔顿量进行了比较。证明了GRECP算子可以从相当自然的物理基础中导出，并从理论上证明了GRECP算子的生成过程。分析了RECP近似在模拟原子价区和外核区的相互作用和密度时的准确性。还研究了用GRECP计算去除内核电子后模拟相互作用的可靠性。额外的非本地条款的重要性与潜在的外核pseudospinor和与潜在的依赖于最外层的核壳的占用数的GRECP运营商的表达式证明在计算上的银，钡，汞，铊，和U原子。研究了外核电位与价电位之间的差异。结果表明，在价区，二分量赝旋量与四分量旋量的大分量在计算同一组态时具有很高的精度。高斯近似所造成的问题，而奇异形状的潜力被认为是。为了达到所需的高精度近似的数值潜力的高斯，严重的额外的努力进行。©1999年约翰威利父子公司。Int J Quant Chem 71：359-401，1999
The generalized relativistic effective core potential (GRECP) method is analyzed from theoretical and computational points of view. The Hamiltonian in the frozen-core approximation is compared with the Hamiltonian containing the GRECP operator. It is demonstrated that the GRECP operator can be derived from rather natural physical grounds and the procedure of the GRECP generation can be justified theoretically. The accuracy of the RECP approximations in the simulation of the interactions and densities in the valence and outer-core regions is analyzed. The reliability of the simulation of the interaction with the inner-core electrons removed from the calculations with the GRECP is also studied. The importance of additional nonlocal terms both with the potentials for the outer-core pseudospinors and with the potentials depending on the occupation numbers of the outermost core shells in the expression for the GRECP operator is demonstrated in calculations on the Ag, Ba, Hg, Tl, and U atoms. The difference between the outer core and valence potentials was investigated. It is shown that in the valence region the two-component pseudospinors coincide with the large components of four-component spinors in calculations for the same configuration states with a very high accuracy. Problems of Gaussian approximation caused by rather singular shapes of the potentials are considered. To attain a required high accuracy of approximation of the numerical potentials by Gaussians, serious additional efforts were undertaken. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 359–401, 1999