An improved DIIS method using a versatile residual matrix to accelerate SCF starting from a crude guess,Journal of Computational Chemistry

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An improved DIIS method using a versatile residual matrix to accelerate SCF starting from a crude guess
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-07-09 , DOI: 10.1002/jcc.27463
Linping Hu ₁ , Yanoar Pribadi Sarwono _{1,

2} , Yonglong Ding ₃ , Fang He ₁ , Rui-Qin Zhang _{1,

3,

4}

Affiliation

The minimization of the commutator of the Fock and density matrices as the error matrix in the direct inversion of the iterative subspace (CDIIS) developed by Pulay is a powerful self-consistent field (SCF) acceleration technique for the construction of optimum Fock matrix, if initiated with a fair initial guess. In this work, we present an alternative minimized error matrix to the commutator in the CDIIS, namely the residual or the gradient of the energy-functional for a Slater determinant subject to the orthonormality constraints among orbitals, representing the search for a newly improved Fock matrix in the direction of the residual in the direct inversion of the iterative subspace (RDIIS). Implemented in the computational chemistry package GAMESS, the RDIIS is compared with the standard CDIIS and the second order SCF orbital optimization (SOSCF) for tested molecules started with a crude guess. As a result, the RDIIS stably and efficiently performs the SCF convergence acceleration. Furthermore, the RDIIS is considerably independent on the subspace size with the concentrated linear coefficients accounting proportionally for the Fock matrices close to the current iteration.

中文翻译：

一种改进的 DIIS 方法，使用多功能残差矩阵从粗略猜测开始加速 SCF

Pulay 开发的迭代子空间（CDIIS）的直接反转中将 Fock 和密度矩阵的换向子最小化作为误差矩阵，如果以公平的初始猜测开始，则是一种强大的自洽场（SCF）加速技术，用于构建最佳 Fock 矩阵。在这项工作中，我们提出了 CDIIS 中换向器的替代最小误差矩阵，即受轨道之间正交约束的 Slater 行列式的能量泛函的残差或梯度，表示在迭代子空间（RDIIS）的直接反转中沿残差方向寻找新改进的 Fock 矩阵。RDIIS 在计算化学包 GAMESS 中实现，与标准 CDIIS 和测试分子的二阶 SCF 轨道优化（SOSCF）进行比较，从粗略猜测开始。因此，RDIIS 可以稳定高效地执行 SCF 收敛加速。此外，RDIIS 在很大程度上与子空间大小无关，集中线性系数按比例考虑接近当前迭代的 Fock 矩阵。

更新日期：2024-07-09

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