Analytic energy gradient of projected Hartree-Fock within projection after variation.
Analytic energy gradient of projected Hartree-Fock within projection after variation.
复制标题
变化后投影内投影 Hartree-Fock 的解析能量梯度。
DOI：
10.1063/1.4978050
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
S. Ten
中科院分区：
文献类型：
--
作者：
Motoyuki Uejima;S. Ten
我们开发了一种几何优化技术的投影后变分（PAV）计划最近改进的投影Hartree-Fock（PHF）作为一个快速的替代变分后投影（VAP）的方法优化的分子/团簇的结构在平均场计算成本的自适应电子态。PHF通过恢复对称性破缺的单参考波函数的对称性来处理非动力学相关效应，并且能够对轨道选择进行黑箱处理。使用HF轨道代替PHF轨道，我们的方法节省了轨道优化的计算成本，避免了VAP方案中有时出现的收敛问题。我们发现，PAV-PHF提供的几何形状与完整的活性空间自洽场和VAP-PHF的测试系统，即CH 2，O3，和[Cu 2 O 2]2+核心，其中非动态相关是丰富的。该方法适用于非动态关联为主的大系统，可以在多个自适应状态中找到稳定结构。
We develop a geometrical optimization technique for the projection-after-variation (PAV) scheme of the recently refined projected Hartree-Fock (PHF) as a fast alternative to the variation-after-projection (VAP) approach for optimizing the structures of molecules/clusters in symmetry-adapted electronic states at the mean-field computational cost. PHF handles the nondynamic correlation effects by restoring the symmetry of a broken-symmetry single reference wavefunction and moreover enables a black-box treatment of orbital selections. Using HF orbitals instead of PHF orbitals, our approach saves the computational cost for the orbital optimization, avoiding the convergence problem that sometimes emerges in the VAP scheme. We show that PAV-PHF provides geometries comparable to those of the complete active space self-consistent field and VAP-PHF for the tested systems, namely, CH2, O3, and the [Cu2O2]2+ core, where nondynamic correlation is abundant. The proposed approach is useful for large systems mainly dominated by nondynamic correlation to find stable structures in many symmetry-adapted states.
影响因子：
4.4
作者：
JENSEN, P;BUNKER, PR
通讯作者：
BUNKER, PR