2019/10/31 by Pierre-François Loos, Pierre‐François Loos, Barthélémy Pradines +3 · 2 citations
Biochemistry, Genetics and Molecular Biology · Chemistry · Materials Science · Mathematics · Physics and Astronomy · #Advanced Chemical Physics Studies #Basis (linear algebra) #Basis function #Basis set #Chemistry #Coulomb #DNA and Nucleic Acid Chemistry #Density functional theory #Electron #Electron density #Electronic correlation #Geometry #Ion #Ionization #Ionization energy #Machine Learning in Materials Science #Mathematics #Nucleobase #Perturbation theory (quantum mechanics) #Physics #Quantum mechanics #Statistical physics #Thymine #cond-mat.str-el #physics.chem-ph #physics.comp-ph
paper · pdf · doi:10.1021/acs.jctc.9b01067
published as J. Chem. Theory Comput. 2020, 16, 1018-1028 · 11 pages, 2 figures (supporting information available)
openalex publication_date 2019/12/31 · arxiv created 2020/01/04 · arxiv updated 2020/06/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
Similar to other electron correlation methods, many-body perturbation theory methods based on Green's functions, such as the so-called GW approximation, suffer from the usual slow convergence of energetic properties with respect to the size of the one-electron basis set. This displeasing feature is due to the lack of explicit electron–electron terms modeling the infamous Kato electron–electron cusp and the correlation Coulomb hole around it. Here, we propose a computationally efficient density-based basis-set correction based on short-range correlation density functionals which significantly speeds up the convergence of energetics toward the complete basis set limit. The performance of this density-based correction is illustrated by computing the ionization potentials of the 20 smallest atoms and molecules of the GW100 test set at the perturbative GW (or G 0 W 0 ) level using increasingly large basis sets. We also compute the ionization potentials of the five canonical nucleobases (adenine, cytosine, thymine, guanine, and uracil) and show that, here again, a significant improvement is obtained.