preprints.org > physical sciences > atomic and molecular physics > doi: 10.20944/preprints202212.0530.v1

Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Version 1 : Received: 18 December 2022 / Approved: 28 December 2022 / Online: 28 December 2022 (07:57:51 CET)

Generalized relativistic pseudopotentials (GRPP) of atomic cores implying the use of different potentials for atomic electronic shells with different principal quantum numbers give rise to accurate and reliable relativistic electronic structure models of atoms, molecules, clusters, and solids. These models readily incorporate the effects of Breit electron-electron interactions and one-loop quantum electrodynamics effects. Here we report the computational procedure for evaluating one-electron integrals of GRPP over contracted Gaussian functions. This procedure was implemented in a library of routines named LIBGRPP, which can be integrated into existing quantum chemistry software, thus enabling the application of various methods to solve the many-electron problem with GRPPs. Pilot applications to electronic transitions in the ThO and UO2 molecules using the new library and intermediate-Hamiltonian Fock space relativistic coupled cluster method are presented. The results clearly demonstrate that rather economical tiny-core GRPP models can exceed in accuracy relativistic all-electron models defined by Dirac-Coulomb and Dirac-Coulomb-Gaunt Hamiltonians.

generalized relativistic pseudopotentials; molecular integrals; Gaussian basis functions; relativistic coupled cluster theory; excited states; heavy-element compounds; high-precision electronic structure modeling; thorium oxide; uranium dioxide.

Physical Sciences, Atomic and Molecular Physics

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