MP2 energy and density for large molecular systems with internal error control using the Divide-Expand-Consolidate scheme

Kasper Kristensen, Ida Marie Høyvik, Branislav Jansik, Poul Jørgensen, Thomas Kjærgaard, Simen Reine, Jacek Jakowski

Research output: Contribution to journalArticlepeer-review

61 Scopus citations

Abstract

Divide-Expand-Consolidate (DEC) is a local correlation method where the inherent locality of the electron correlation problem is used to express the correlated calculation on a large molecular system in terms of small independent fragment calculations employing small subsets of local HF orbitals. A crucial feature of the DEC scheme is that the sizes of the local orbital spaces are determined in a black box manner during the calculation. In this way it is ensured that the correlation energy has been determined to a predefined precision compared to a conventional calculation. In the present work we apply the DEC scheme to calculate the correlation energy as well as the electron density matrix for the insulin molecule using second order Moller-Plesset (MP2) theory. This is the first DEC calculation on a molecular system which is too large to be treated using a conventional MP2 implementation. The fragmentation errors for the insulin DEC calculation are carefully analyzed using internal consistency checks. It is demonstrated that size-intensive properties are determined to the same precision for small and large molecules. For example, the percentage of correlation energy recovered and the error per electron in the correlated density matrix depend only on the predefined precision and not on the molecular size.

Original languageEnglish
Pages (from-to)15706-15714
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number45
DOIs
StatePublished - Dec 5 2012
Externally publishedYes

Funding

FundersFunder number
Seventh Framework Programme0919436, 291371

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