We present an integration scheme for optimizing the orbitals in numerical electronic structure calculations on general molecules. The orbital optimization is performed by integrating the Helmholtz kernel in the double bubble and cube basis, where bubbles represent the steep part of the functions in the vicinity of the nuclei, whereas the remaining cube part is expanded on an equidistant three-dimensional grid. The bubbles' part is treated by using one-center expansions of the Helmholtz kernel in spherical harmonics multiplied with modified spherical Bessel functions of the first and second kinds. The angular part of the bubble functions can be integrated analytically, whereas the radial part is integrated numerically. The cube part is integrated using a similar method as we previously implemented for numerically integrating two-electron potentials. The behavior of the integrand of the auxiliary dimension introduced by the integral transformation of the Helmholtz kernel has also been investigated. The correctness of the implementation has been checked by performing Hartree-Fock self-consistent-field calculations on H, HO, and CO. The obtained energies are compared with reference values in the literature showing that an accuracy of 10 to 10 E can be obtained with our approach.

A grid-based fast multipole method (GB-FMM) for optimizing three-dimensional (3D) numerical molecular orbitals in the bubbles and cube double basis has been developed and implemented. The present GB-FMM method is a generalization of our recently published GB-FMM approach for numerically calculating electrostatic potentials and two-electron interaction energies. The orbital optimization is performed by integrating the Helmholtz kernel in the double basis. The steep part of the functions in the vicinity of the nuclei is represented by one-center bubbles functions, whereas the remaining cube part is expanded on an equidistant 3D grid. The integration of the bubbles part is treated by using one-center expansions of the Helmholtz kernel in spherical harmonics multiplied with modified spherical Bessel functions of the first and second kind, analogously to the numerical inward and outward integration approach for calculating two-electron interaction potentials in atomic structure calculations. The expressions and algorithms for massively parallel calculations on general purpose graphics processing units (GPGPU) are described. The accuracy and the correctness of the implementation has been checked by performing Hartree-Fock self-consistent-field calculations (HF-SCF) on H, HO, and CO. Our calculations show that an accuracy of 10 to 10 E can be reached in HF-SCF calculations on general molecules.

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Density functional theory within the Kohn–Sham density functional theory (KS-DFT) ansatz has been implemented into our bubbles and cube real-space molecular electronic structure framework, where functions containing steep cusps in the vicinity of the nuclei are expanded in atom-centered one-dimensional (1D) numerical grids multiplied with spherical harmonics (bubbles). The remainder, i.e., the cube, which is the cusp-free and smooth difference between the atomic one-center contributions and the exact molecular function, is represented on a three-dimensional (3D) equidistant grid by using a tractable number of grid points. The implementation of the methods is demonstrated by performing 3D numerical KS-DFT calculations on light atoms and small molecules. The accuracy is assessed by comparing the obtained energies with the best available reference energies.