论文标题

两电子积分在量子化学计算中使用扰动或有限磁场的潮汐分解,包括原子轨道

Cholesky decomposition of two-electron integrals in quantum-chemical calculations with perturbative or finite magnetic fields using gauge-including atomic orbitals

论文作者

Gauss, Jürgen, Blaschke, Simon, Burger, Sophia, Nottoli, Tommaso, Lipparini, Filippo, Stopkowicz, Stella

论文摘要

在使用有限或扰动的磁场以及包括原子轨道的量子化计算的情况下,对两电子积分的使用Cholesky分解(CD)进行了严格分析。我们特别研究了如何在此类计算中解释置换对称性,以及如何利用这种对称性以减少计算要求。建议针对有限场案例进行修改的CD程序,该方法将存储器的存储器对存储的存储大致减半。 Cholesky载体的最终对称性也可以节省计算成本。对于触发磁场的衍生两电子积分,我们通过以无场为参考点的无现场情况为参考点的相应有限磁场公式的一阶taylor扩展来得出CD表达式。被扰动的cholesky载体被证明是反对称的(如Burger等人已经提出的(J.Chem。Phys。,155,074105(2021)(2021))),相应的表达能够在所需的积分评估中获得大量节省(通过一个人的实际构造,以及在cholesy的实际结构中(通过cholesy的实际结构)(通过一个两者的构建)(由一定的构建中)。 (J.Chem。Phys。,150,194112(2019))和Zhang等人(J.Phys。Chem。A,125,4258-4265(2021))。涉及数百个基础功能的病例的数值示例在有限和扰动磁场的情况下验证了有关CD的建议。

A rigorous analysis is carried out concerning the use of Cholesky decomposition (CD) of two-electron integrals in the case of quantum-chemical calculations with finite or perturbative magnetic fields and gauge-including atomic orbitals. We investigate in particular how permutational symmetry can be accounted for in such calculations and how this symmetry can be exploited to reduce the computational requirements. A modified CD procedure is suggested for the finite-field case that roughly halves the memory demands for the storage of the Cholesky vectors. The resulting symmetry of the Cholesky vectors also enables savings in the computational costs. For the derivative two-electron integrals in case of a perturbative magnetic field we derive CD expressions by means of a first-order Taylor expansion of the corresponding finite magnetic-field formulas with the field-free case as reference point. The perturbed Cholesky vectors are shown to be antisymmetric (as already proposed by Burger et al. (J. Chem. Phys., 155, 074105 (2021))) and the corresponding expressions enable significant savings in the required integral evaluations (by a factor of about four) as well as in the actual construction of the Cholesky vectors (by means of a two-step procedure similar to the one presented by Folkestad et al. (J. Chem. Phys., 150, 194112 (2019)) and Zhang et al. (J. Phys. Chem. A, 125, 4258-4265 (2021))). Numerical examples with cases involving several hundred basis functions verify our suggestions concerning CD in case of finite and perturbative magnetic fields.

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