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

Urban, Lars; Laqua, Henryk und Ochsenfeld, Christian (2022): Highly Efficient and Accurate Computation of Multiple Orbital Spaces Spanning Fock Matrix Elements on Central and Graphics Processing Units for Application in F12 Theory. In: Journal of Chemical Theory and Computation, Bd. 18, Nr. 7: S. 4218-4228

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 snLinK 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 (similar to 1 mH) even for the coarsest settings and can easily be reduced below 1 mu H 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(N-bas(2)) instead of O(N-bas(4)) 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-zeta F12 basis set (5058 AO basis functions, 9267 CABS basis functions) is accelerated over 1575x using CPUs and over 4155x employing GPUs.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1549-9618
• Sprache: Englisch