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Embedded density functional theory for covalently bonded and strongly interacting subsystems

Goodpaster, Jason D. and Barnes, Taylor A. and Miller, Thomas F., III (2011) Embedded density functional theory for covalently bonded and strongly interacting subsystems. Journal of Chemical Physics, 134 (16). Art. No. 164108. ISSN 0021-9606.

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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, CH_3–CF_3, 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.

Item Type:Article
Related URLs:
URLURL TypeDescription PublisherArticle
Goodpaster, Jason D.0000-0001-6461-4501
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2011 American Institute of Physics. Received 20 February 2011; accepted 6 April 2011; published online 28 April 2011. 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.
Funding AgencyGrant Number
Army Research Laboratory (ARL)UNSPECIFIED
Army Research Office (ARO)W911NF-10-1-0202
Office of Naval Research (ONR)N00014-10-1-0884
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Subject Keywords:beryllium, density functional theory, dissociation energies, lithium, molecular clusters, molecular electronic states, organic compounds, potential energy surfaces, water
Issue or Number:16
Classification Code:PACS: 31.15.E-; 31.50.-x; 33.15.Fm; 36.40.Cg
Record Number:CaltechAUTHORS:20110525-151024690
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23801
Deposited By: Tony Diaz
Deposited On:17 Jun 2011 17:55
Last Modified:09 Mar 2020 13:18

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