Mullinax J Wayne, Sokolov Alexander Yu, Schaefer Henry F
Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
J Chem Theory Comput. 2015 Jun 9;11(6):2487-95. doi: 10.1021/acs.jctc.5b00346.
We evaluate the performance of density cumulant functional theory (DCT) for capturing static correlation effects. In particular, we examine systems with significant multideterminant character of the electronic wave function, such as the beryllium dimer, diatomic carbon, m-benzyne, 2,6-pyridyne, twisted ethylene, as well as the barrier for double-bond migration in cyclobutadiene. We compute molecular properties of these systems using the ODC-12 and DC-12 variants of DCT and compare these results to multireference configuration interaction and multireference coupled-cluster theories, as well as single-reference coupled-cluster theory with single, double (CCSD), and perturbative triple excitations [CCSD(T)]. For all systems the DCT methods show intermediate performance between that of CCSD and CCSD(T), with significant improvement over the former method. In particular, for the beryllium dimer, m-benzyne, and 2,6-pyridyne, the ODC-12 method along with CCSD(T) correctly predict the global minimum structures, while CCSD predictions fail qualitatively, underestimating the multireference effects. Our results suggest that the DC-12 and ODC-12 methods are capable of describing emerging static correlation effects but should be used cautiously when highly accurate results are required. Conveniently, the appearance of multireference effects in DCT can be diagnosed by analyzing the DCT natural orbital occupations, which are readily available at the end of the energy computation.
我们评估了密度累积量泛函理论(DCT)捕捉静态相关效应的性能。具体而言,我们研究了具有显著多行列式特征电子波函数的体系,如铍二聚体、双原子碳、间苯炔、2,6 - 吡啶炔、扭曲乙烯,以及环丁二烯中双键迁移的势垒。我们使用DCT的ODC - 12和DC - 12变体计算这些体系的分子性质,并将这些结果与多参考组态相互作用和多参考耦合簇理论,以及具有单、双(CCSD)和微扰三重激发的单参考耦合簇理论[CCSD(T)]进行比较。对于所有体系,DCT方法的性能介于CCSD和CCSD(T)之间,相对于前一种方法有显著改进。特别是对于铍二聚体、间苯炔和2,6 - 吡啶炔,ODC - 12方法与CCSD(T)一起正确预测了全局最小结构,而CCSD的预测在定性上失败,低估了多参考效应。我们的结果表明,DC - 12和ODC - 12方法能够描述新出现的静态相关效应,但在需要高精度结果时应谨慎使用。方便的是,DCT中多参考效应的出现可以通过分析DCT自然轨道占据情况来诊断,这些在能量计算结束时很容易获得。