Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations.
Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations.
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使用精确的耦合簇计算对旋转 g 张量和磁化率的密度泛函理论计算进行基准测试。
DOI：
10.1063/1.3242081
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
J. Gauss
中科院分区：
文献类型：
--
作者：
O. Lutnaes;A. M. Teale;T. Helgaker;D. Tozer;K. Ruud;J. Gauss
用耦合团簇单双（CCSD）理论和耦合团簇单双微扰三重（CCSD（T））理论，在由（转动）伦敦原子轨道组成的各种基组中，计算了一组精确的基准转动g张量和磁化率.通过与实验数据仔细比较，考虑到零点振动修正，建立了旋转g张量的结果的准确性。在对所采用的基本数据集进行分析之后，采用外推技术来提供基本数据集极限数量的估计数，从而建立一个准确的基准数据集。通过检查各种各样的密度泛函的计算这些属性的数据集的效用证明。没有一种密度泛函方法能与CCSD或CCSD（T）方法竞争。清楚地说明了仔细考虑振动效应的必要性。最后，纯耦合簇的结果进行了比较，密度泛函计算的结果约束，以得到相同的电子密度。在交换相关泛函的电流依赖的重要性进行了讨论，在这种比较。
An accurate set of benchmark rotational g tensors and magnetizabilities are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster single-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the results obtained is established for the rotational g tensors by careful comparison with experimental data, taking into account zero-point vibrational corrections. After an analysis of the basis sets employed, extrapolation techniques are used to provide estimates of the basis-set-limit quantities, thereby establishing an accurate benchmark data set. The utility of the data set is demonstrated by examining a wide variety of density functionals for the calculation of these properties. None of the density-functional methods are competitive with the CCSD or CCSD(T) methods. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of density-functional calculations constrained to give the same electronic density. The importance of current dependence in exchange-correlation functionals is discussed in light of this comparison.