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Benchmarking the accuracy of the separable resolution of the identity approach for correlated methods in the numeric atom-centered orbitals framework

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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en

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15

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Journal of Chemical Physics, Volume 160, issue 2, pp. 1-15

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Four-center two-electron Coulomb integrals routinely appear in electronic structure algorithms. The resolution-of-the-identity (RI) is a popular technique to reduce the computational cost for the numerical evaluation of these integrals in localized basis-sets codes. Recently, Duchemin and Blase proposed a separable RI scheme [J. Chem. Phys. 150, 174120 (2019)], which preserves the accuracy of the standard global RI method with the Coulomb metric and permits the formulation of cubic-scaling random phase approximation (RPA) and GW approaches. Here, we present the implementation of a separable RI scheme within an all-electron numeric atom-centered orbital framework. We present comprehensive benchmark results using the Thiel and the GW100 test set. Our benchmarks include atomization energies from Hartree-Fock, second-order Møller-Plesset (MP2), coupled-cluster singles and doubles, RPA, and renormalized second-order perturbation theory, as well as quasiparticle energies from GW. We found that the separable RI approach reproduces RI-free HF calculations within 9 meV and MP2 calculations within 1 meV. We have confirmed that the separable RI error is independent of the system size by including disordered carbon clusters up to 116 atoms in our benchmarks.

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| openaire: EC/H2020/951786/EU//NOMAD CoE

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Delesma, F, Leucke, M, Golze, D & Rinke, P 2024, 'Benchmarking the accuracy of the separable resolution of the identity approach for correlated methods in the numeric atom-centered orbitals framework', Journal of Chemical Physics, vol. 160, no. 2, 024118, pp. 1-15. https://doi.org/10.1063/5.0184406

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