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Embedded Mean-Field Theory with Block-Orthogonalized Partitioning

Ding, Feizhi and Manby, Frederick R. and Miller, Thomas F., III (2017) Embedded Mean-Field Theory with Block-Orthogonalized Partitioning. Journal of Chemical Theory and Computation, 13 (4). pp. 1605-1615. ISSN 1549-9618. doi:10.1021/acs.jctc.6b01065.

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Embedded mean-field theory (EMFT) provides a simple, flexible framework for describing subsystems at different levels of mean-field theory. Subsystems are defined by partitioning a one-particle basis set, with a natural choice being the atomic orbital (AO) basis. Although generally well behaved, EMFT with AO partitioning can exhibit unphysical collapse of the self-consistent solution. To avoid this issue, we introduce subsystem partitioning of a block-orthogonalized (BO) basis set; this eliminates the unphysical collapse without significantly increasing computational cost. We also investigate a non-self-consistent implementation of EMFT, in which the density matrix is obtained using BO partitioning and the final energy evaluated using AO partitioning; this density-corrected EMFT approach is found to yield more accurate energies than BO partitioning while also avoiding issues of the unphysical collapse. Using these refined implementations of EMFT, previously proposed descriptions of the exact-exchange coupling between subsystems are compared: although the EX1 coupling scheme is slightly more accurate than EX0, the small improvement does not merit its substantially greater computational cost.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2017 American Chemical Society. Received 1 November 2016. Published online 28 February 2017. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. Additionally, T.F.M. acknowledges support from a Camille Dreyfus Teacher-Scholar Award, and F.R.M. acknowledges funding from EPSRC (EP/M013111/1). The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Camille and Henry Dreyfus FoundationUNSPECIFIED
Engineering and Physical Sciences Research Council (EPSRC)EP/M013111/1
Issue or Number:4
Record Number:CaltechAUTHORS:20170320-094437871
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Official Citation:Embedded Mean-Field Theory with Block-Orthogonalized Partitioning Feizhi Ding, Frederick R. Manby, and Thomas F. Miller, III Journal of Chemical Theory and Computation 2017 13 (4), 1605-1615 DOI: 10.1021/acs.jctc.6b01065
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75233
Deposited By: Ruth Sustaita
Deposited On:20 Mar 2017 17:24
Last Modified:15 Nov 2021 16:31

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