Highly Efficient and Accurate Computation of Multiple Orbital Spaces Spanning Fock Matrix Elements on Central and Graphics Processing Units for Application in F12 Theory.

Abstract

We employ our recently published highly efficient seminumerical exchange (sn-LinK) [Laqua, H.; Thompson, T. H.; Kussmann, J.; Ochsenfeld, C. J. Chem. Theory Comput. 2020, 16, 1456-1468] and integral-direct resolution of the identity Coulomb (RI-J) [Kussmann, J.; Laqua, H.; Ochsenfeld, C. J. Chem. Theory Comput. 2021, 17, 1512-1521] methods to significantly accelerate the computation of the demanding multiple orbital spaces spanning Fock matrix elements present in R12/F12 theory on central and graphics processing units. The errors introduced by RI-J and sn-LinK into the RI-MP2-F12 energy are thoroughly assessed for a variety of basis sets and integration grids. We find that these numerical errors are always below "chemical accuracy" (∼1 mH) even for the coarsest settings and can easily be reduced below 1 μH by employing only moderately large integration grids and RI-J basis sets. Since the number of basis functions of the multiple orbital spaces is notably larger compared with conventional Hartree-Fock theory, the efficiency gains from the superior basis scaling of RI-J and sn-LinK (O(Nbas2) instead of O(Nbas4) for both) are even more significant, with maximum speedup factors of 37 000 for RI-J and 4500 for sn-LinK. In total, the multiple orbital spaces spanning Fock matrix evaluation of the largest tested structure using a triple-ζ F12 basis set (5058 AO basis functions, 9267 CABS basis functions) is accelerated over 1575× using CPUs and over 4155× employing GPUs.