Resolution-of-the-identity second-order MOller-Plesset perturbation theory with complex basis functions: Benchmark calculations and applications to strong-field ionization of polyacenes

Vera, Mario Hernandez und Jagau, Thomas-C. (2020): Resolution-of-the-identity second-order MOller-Plesset perturbation theory with complex basis functions: Benchmark calculations and applications to strong-field ionization of polyacenes. In: Journal of Chemical Physics, Bd. 152, Nr. 17, 174103

Abstract

We study the performance of the resolution-of-the-identity (RI) approximation for complex basis functions that we recently introduced [M. Hernandez Vera and T.-C. Jagau, J. Chem. Phys. 151, 111101 (2019)] for second-order MOller-Plesset (MP2) perturbation theory as well as for the Coulomb and exchange contributions in Hartree-Fock theory. The sensitivity of this new RI-MP2 method toward the basis set and the auxiliary basis set is investigated, and computation times are analyzed. We show that the auxiliary basis set can be chosen purely real, that is, no complex-scaled functions need to be included. This approximation enables a further speedup of the method without compromising accuracy. We illustrate the application range of our implementation by computing static-field ionization rates of several polyacenes up to pentacene (C22H18) at the RI-MP2 level of theory. Pronounced anisotropies are observed for the ionization rates of these molecules.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 0021-9606
• Sprache: Englisch