Embedded density functional theory for covalently bonded and strongly interacting subsystems

Jason D. Goodpaster, Taylor A. Barnes, Thomas F. Miller

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Embedded density functional theory (e-DFT) is used to describe the electronic structure of strongly interacting molecular subsystems. We present a general implementation of the Exact Embedding (EE) method [J. Chem. Phys. 133, 084103 (2010)] to calculate the large contributions of the nonadditive kinetic potential (NAKP) in such applications. Potential energy curves are computed for the dissociation of Li+-Be, CH3-CF3, and hydrogen-bonded water clusters, and e-DFT results obtained using the EE method are compared with those obtained using approximate kinetic energy functionals. In all cases, the EE method preserves excellent agreement with reference Kohn-Sham calculations, whereas the approximate functionals lead to qualitative failures in the calculated energies and equilibrium structures. We also demonstrate an accurate pairwise approximation to the NAKP that allows for efficient parallelization of the EE method in large systems; benchmark calculations on molecular crystals reveal ideal, size-independent scaling of wall-clock time with increasing system size.

Original languageEnglish (US)
Article number164108
JournalJournal of Chemical Physics
Issue number16
StatePublished - Apr 28 2011

Bibliographical note

Funding Information:
This work is supported by the U.S. Army Research Laboratory (USARL) and the U. S. Army Research Office (USARO) under Grant No. W911NF-10-1-0202 and by the U. S. Office of Naval Research (USONR) under Grant No. N00014-10-1-0884. T.A.B. acknowledges support from a National Defense Science and Engineering Graduate Fellowship, and T.F.M. acknowledges support from a Camille and Henry Dreyfus Foundation New Faculty Award and an Alfred P. Sloan Foundation Research Fellowship.


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