Assessment of the "6-31+G** + LANL2DZ" mixed basis set coupled with density functional theory methods and the effective core potential: prediction of heats of formation and ionization potentials for first-row-transition-metal complexes.
Assessment of the "6-31+G** + LANL2DZ" mixed basis set coupled with density functional theory methods and the effective core potential: prediction of heats of formation and ionization potentials for first-row-transition-metal complexes.
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DOI：
10.1021/jp807643p
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发表时间：
2009-09-10
期刊：
影响因子：
--
通讯作者：
Merz KM Jr
中科院分区：
文献类型：
--
作者：
Yang Y;Weaver MN;Merz KM Jr
长期以来，计算化学家一直对寻找可靠和准确地预测含过渡金属络合物的分子性质的方法表现出极大的兴趣。这份手稿是我们对密度泛函理论(DFT)方法在应用于含过渡金属体系时的验证工作的延续(K.E.Riley；K.M.Merz，Jr.J.Phys.化学。2007、111、6044-6053)。在我们以前的工作中，我们使用全电子基组来研究密度泛函，但结合有效核心势的方法在减少计算成本方面是有效的。考虑到这一点，我们的努力被扩展到包括对所推导的基集的性能的评估，以近似这样的方法以及在相同的密度泛函集上。事实上，对过渡金属采用ECP基团，如LANL2DZ，同时对所有其他非过渡金属原子使用全电子基组，在含过渡金属体系的计算中已变得越来越流行。在这项研究中，我们评估了12个不同的DFT泛函，分别来自GGA，杂化-GGA，META-GGA和杂化-META-GGA类，以及6-31+G**+LANL2DZ(基于过渡金属)混合基组，预测了94和58个系统的两个重要的分子性质：生成热和电离势，它们都位于元素周期表的第三行。值得注意的是，在密度泛函方法中引入精确的交换项通常提高了杂化-GGA方法的电离势预测的精度，但降低了所有杂化密度泛函方法确定过渡金属络合物生成热的可靠性。混合GGA泛函B3LYP对电离势的预测效果最好，而Meta-GGA泛函TPSSTPSS为生成热的计算提供了最可靠和准确的结果。TPSSTPSS是一种从第一性原理出发构造的准GGA泛函，它像从头算一样受到已知的严格约束，成功地预测了含过渡金属体系的电离势和生成热。
Computational chemists have long demonstrated great interest in finding ways to reliably and accurately predict the molecular properties for transition metal containing complexes. This manuscript is a continuation of our validation efforts of Density Functional Theory (DFT) methods when applied to transition metal containing systems (K. E. Riley; K. M. Merz, Jr. J. Phys. Chem. 2007, 111, 6044–6053). In our previous work we examined DFT using all-electron basis sets, but approaches incorporating effective core potentials (ECPs) are effective in reducing computational expense. With this in mind, our efforts were expanded to include evaluation of the performance of the basis set derived to approximate such an approach as well on the same set of density functionals. Indeed, employing an ECP basis such as LANL2DZ for transition metals, while using all-electron basis sets for all other non-transition-metal atoms has become more and more popular in computations on transition metal containing systems. In this study, we assess the performance of twelve different DFT functionals, from GGA, hybrid-GGA, meta-GGA and hybrid-meta-GGA classes respectively, along with the 6–31+G** + LANL2DZ (on the transition metal) mixed basis set on predicting two important molecular properties: heats of formation and ionization potentials, for 94 and 58 systems containing first row transition metals from Ti to Zn, which are all in the third row of the periodic table. An interesting note is that the inclusion of the exact exchange term in density functional methods generally increases the accuracy of ionization potentials prediction for the hybrid-GGA methods but decreases the reliability of determining the heats of formation for transition metal containing complexes for all hybrid density functional methods. The hybrid-GGA functional B3LYP gives the best performance on predicting the ionization potentials while the meta-GGA functional TPSSTPSS provides the most reliable and accurate results for heats of formation calculations. TPSSTPSS, a meta-GGA functional, which was constructed from first principles and subject to known exact constraints just like in an “ab initio” way, is successful in predicting both the ionization potentials and the heats of formation for transition metal containing systems.
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