Correcting Basis Set Incompleteness in Wave Function Correlation Energy by Dressing Electronic Hamiltonian with an Effective Short-Range Interaction
Michał Hapka, Aleksandra Tucholska, Marcin Modrzejewski, Pavlo Golub, Libor Veis, Katarzyna Pernal
TL;DR
This paper introduces a new method to reduce errors in electron correlation energy calculations caused by incomplete basis sets.
Contribution
A novel approach to basis set incompleteness error correction is proposed, avoiding reliance on short-range correlation density functionals.
Findings
The method modifies the electron interaction operator with an effective short-range interaction.
Encouraging results were obtained for relative energies of test molecules using complete active space wave functions.
Abstract
We propose a general approach to reducing basis set incompleteness error in electron correlation energy calculations. The correction is computed alongside the correlation energy in a single calculation by modifying the electron interaction operator with an effective short-range electron–electron interaction. Our approach is based on a local mapping between the Coulomb operator projected onto a finite basis and a long-range interaction represented by the error function with a local range-separated parameter, originally introduced by Giner et al. [ J. Chem. Phys. 2018, 149, 194301 30466264 10.1063/1.5052714]. Unlike the basis set incompleteness error correction proposed in that work, our method does not rely on short-range correlation density functionals. As a numerical demonstration, we apply the method with complete active space wave functions. Correlation energies are computed using…
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Taxonomy
TopicsSpectroscopy and Quantum Chemical Studies · Quantum, superfluid, helium dynamics · Advanced Chemical Physics Studies