arXiv:cond-mat/0606115 · The Journal of Chemical Physics

Multireference correlation in long molecules with the quadratic scaling density matrix renormalization group

Johannes Hachmann, Wim Cardoen, Garnet Kin‐Lic Chan

Published Oct 8, 2006• 199 citations

Abstract

We have devised a local ab initio density matrix renormalization group algorithm to describe multireference correlations in large systems. For long molecules that are extended in one of their spatial dimensions, we can obtain an exact characterization of correlation, in the given basis, with a cost that scales only quadratically with the size of the system. The reduced scaling is achieved solely through integral screening and without the construction of correlation domains. We demonstrate the scaling, convergence, and robustness of the algorithm in polyenes and hydrogen chains. We converge to exact correlation energies (in the sense of full configuration interaction, with 1-10 microE(h) precision) in all cases and correlate up to 100 electrons in 100 active orbitals. We further use our algorithm to obtain exact energies for the metal-insulator transition in hydrogen chains and compare and contrast our results with those from conventional quantum chemical methods.

DOI: 10.1063/1.2345196

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