Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes

Jason D. Goodpaster, Taylor A. Barnes, Frederick R. Manby, Thomas F. Miller

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Abstract

Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the accuracy and stability of WFT-in-DFT embedding calculations. In particular, we develop spin-dependent embedding potentials in both restricted and unrestricted orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and develop an orbital-occupation-freezing technique to improve the convergence of optimized effective potential calculations that arise in the evaluation of the embedding potential. The new techniques are demonstrated in applications to the van-der-Waals-bound ethylene-propylene dimer and to the hexa-aquairon(II) transition-metal cation. Calculation of the dissociation curve for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating errors in the dispersion interactions due to conventional exchange-correlation (XC) functionals while simultaneously avoiding errors due to subsystem partitioning across covalent bonds. Application of WFT-in-DFT embedding to the calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II) cation reveals that the majority of the dependence on the DFT XC functional can be eliminated by treating only the single transition-metal atom at the WFT level; furthermore, these calculations demonstrate the substantial effects of open-shell contributions to the embedding potential, and they suggest that restricted open-shell WFT-in-DFT embedding provides better accuracy than unrestricted open-shell WFT-in-DFT embedding due to the removal of spin contamination.

Original languageEnglish (US)
Article number224113
JournalJournal of Chemical Physics
Volume137
Issue number22
DOIs
StatePublished - Dec 14 2012

Bibliographical note

Funding Information:
This work is supported in part by the Air Force Office of Scientific Research (FA9550-11-1-0288) and the U. S. Army Research Laboratory and the U. S. Army Research Office (W911NF-10-1-0202). T.F.M. and F.R.M. also gratefully acknowledge network funding from the NSF (CHE-1057112) and EPSRC (EP/J012742/1), respectively. Computational resources were provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy (Contract No. DE-AC02-05CH11231).

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