Low-scaling first-order properties within second-order Møller-Plesset perturbation theory using Cholesky decomposed density matrices

An efficient implementation of energy gradients and of hyperfine coupling constants in second-order Møller-Plesset perturbation theory (MP2) is presented based on our fully atomic orbital (AO)-based approach. For the latter, an unrestricted AO-based MP2 formulation is introduced. A reduction in the...

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Veröffentlicht in:The Journal of chemical physics 2017-07, Vol.147 (2), p.024101-024101
Hauptverfasser: Vogler, Sigurd, Ludwig, Martin, Maurer, Marina, Ochsenfeld, Christian
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Sprache:eng
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Zusammenfassung:An efficient implementation of energy gradients and of hyperfine coupling constants in second-order Møller-Plesset perturbation theory (MP2) is presented based on our fully atomic orbital (AO)-based approach. For the latter, an unrestricted AO-based MP2 formulation is introduced. A reduction in the dependency of the computational efficiency on the size of the basis set is achieved by a Cholesky decomposition and the prefactor is reduced by the resolution-of-the-identity approximation. Significant integral contributions are selected based on distance-including integral estimates (denoted as QQR-screening) and its reliability as a fully controlled screening procedure is demonstrated. The rate-determining steps are shown via model computations to scale cubically in the computation of energy gradients and quadratically in the case of hyperfine coupling constants. Furthermore, a significant speed-up of the computational time with respect to the canonical formulation is demonstrated.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4990413