Construction and application of a new dual-hybrid random phase approximation.
Construction and application of a new dual-hybrid random phase approximation.
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新型双混合随机相位逼近的构建与应用。
DOI：
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发表时间：
2015
影响因子：
5.5
通讯作者：
Mihály Kállay
中科院分区：
文献类型：
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作者：
P. Mezei;G. Csonka;A. Ruzsinszky;Mihály Kállay
直接随机相近似(DRPA)与Kohn-Sham参考轨道相结合是计算化学中最有前途的工具之一，在化学和物理的许多领域都有应用。这是因为它随系统大小的变化为N(4)，这比标准耦合团簇等精确的从头算波函数方法有相当大的优势。与标准的密度泛函理论方法相比，DRPA对热力学和电子性质的描述也更加准确。它还能够描述很强的静态电子关联效应，即使在通常的单参考方法遗漏的小带隙或消失的大系统中也是如此。然而，由于其自相关误差，DRPA有几个缺陷。为了获得准确和精确的反应能、势垒以及非共价态的分子内和分子间相互作用，我们构造了一种新的双杂化DRPA(精确和半局域交换在能量和轨道上的杂交)，并测试了这种新泛函在等轴线、等轴线、亚均线、同线和超线反应类上的性能。我们还使用了14个Diels-Alder反应、6个雾化能(AE6)、38个碳氢原子化能和100个反应势垒高度(DBH24、HT-BH38和NHT-BH38)的测试集。对于非共价化合物，我们使用NCCE31和S22测试集。为了测试分子内相互作用，我们使用了一组烷烃、半胱氨酸、苯丙氨酸-甘氨酸-甘氨酸三肽和单糖构象。我们还讨论了离域误差和静态相关误差。我们表明，在计算参考轨道和最终能量时，75%的大的精确交换混合可以提供对化学性质的普遍准确的描述。
The direct random phase approximation (dRPA) combined with Kohn-Sham reference orbitals is among the most promising tools in computational chemistry and applicable in many areas of chemistry and physics. The reason for this is that it scales as N(4) with the system size, which is a considerable advantage over the accurate ab initio wave function methods like standard coupled-cluster. dRPA also yields a considerably more accurate description of thermodynamic and electronic properties than standard density-functional theory methods. It is also able to describe strong static electron correlation effects even in large systems with a small or vanishing band gap missed by common single-reference methods. However, dRPA has several flaws due to its self-correlation error. In order to obtain accurate and precise reaction energies, barriers and noncovalent intra- and intermolecular interactions, we construct a new dual-hybrid dRPA (hybridization of exact and semilocal exchange in both the energy and the orbitals) and test the performance of this new functional on isogyric, isodesmic, hypohomodesmotic, homodesmotic, and hyperhomodesmotic reaction classes. We also use a test set of 14 Diels-Alder reactions, six atomization energies (AE6), 38 hydrocarbon atomization energies, and 100 reaction barrier heights (DBH24, HT-BH38, and NHT-BH38). For noncovalent complexes, we use the NCCE31 and S22 test sets. To test the intramolecular interactions, we use a set of alkane, cysteine, phenylalanine-glycine-glycine tripeptide, and monosaccharide conformers. We also discuss the delocalization and static correlation errors. We show that a universally accurate description of chemical properties can be provided by a large, 75% exact exchange mixing both in the calculation of the reference orbitals and the final energy.
影响因子：
4.4
作者：
Janesko, Benjamin G.;Scuseria, Gustavo E.
通讯作者：
Scuseria, Gustavo E.
影响因子：
15
作者：
Wheeler, Steven E.;Houk, Kendall N.;Schleyer, Paul V. R.;Allen, Wesley D.
通讯作者：
Allen, Wesley D.