论文标题
在水簇阴离子上,自我交流删除在密度功能计算中的重要性
Importance of self-interaction-error removal in density functional calculations on water cluster anions
论文作者
论文摘要
对于标准的半局部和(全局)混合密度近似值(DFAS),对水簇阴离子中的过量电荷的准确描述具有挑战性。利用使用Fermi-Löwdin轨道的Perdew-Zunger自我交织校正(SIC)方法的最新单一不变实施,我们评估自相互作用误差对水簇垂直脱离能量的影响,与局部旋转密度近似(LSDA)的垂直脱离能量(perdew-berke-interization cortialtional and cortially commination and cortially commination)(Pbeimentation)(Pbeimentation)(Pbeimentiant)(Pbeimentation)适当规范(扫描)元gga功能。我们的结果表明,对于异构体的相对能量相对于参考CCSD(t)值,未校正的扫描功能的偏差最小为21 MEV,比对于MP2方法的偏差要好。 SIC-SCAN的性能与MP2的性能相当,并且比SIC-LSDA和SIC-PBE更好,但它逆转了两个最低异构体的水己酰阴离子的排序。消除自我交互误差(SIE)纠正了LSDA,PBE和扫描的趋势,以超过额外的电子。从相应阴离子和中性簇的总能量差异获得的水簇阴离子的垂直脱离能(VDE)可以通过消除自我相互作用而显着改善,并且比混合B3LYP功能更好,但降低了MP2精度。去除SIE会导致额外电子特征值的位置大大改善。 SIC之后,最高占用特征值的负阴性为VDE提供了极好的近似值,尤其是对于SIC-PBE而言,相对于CCSD(T)的平均绝对误差仅为17 MeV,这是这项工作中所有近似值中最好的。
Accurate description of the excess charge in water cluster anions is challenging for standard semi-local and (global) hybrid density functional approximations (DFAs). Using the recent unitary invariant implementation of the Perdew-Zunger self-interaction correction (SIC) method using Fermi-Löwdin orbitals, we assess the effect of self-interaction error on the vertical detachment energies of water clusters anions with the local spin density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation, and the strongly constrained and appropriately normed (SCAN) meta-GGA functionals. Our results show that for the relative energies of isomers with respect to reference CCSD(T) values, the uncorrected SCAN functional has the smallest deviation of 21 meV, better than that for the MP2 method. The performance of SIC-SCAN is comparable to that of MP2 and is better than SIC-LSDA and SIC-PBE, but it reverses the ordering of the two lowest isomers for water hexamer anions. Removing self interaction error (SIE) corrects the tendency of LSDA, PBE, and SCAN to over-bind the extra electron. The vertical detachment energies (VDEs) of water cluster anions, obtained from the total energy differences of corresponding anion and neutral clusters, are significantly improved by removing self-interaction and are better than the hybrid B3LYP functional, but fall short of MP2 accuracy. Removing SIE results in substantial improvement in the position of the eigenvalue of the extra electron. The negative of the highest occupied eigenvalue after SIC provides an excellent approximation to the VDE, especially for SIC-PBE where the mean absolute error with respect to CCSD(T) is only 17 meV, the best among all approximations compared in this work.