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Even-handed subsystem selection in projection-based embedding

Welborn, Matthew and Manby, Frederick R. and Miller, Thomas F., III (2018) Even-handed subsystem selection in projection-based embedding. Journal of Chemical Physics, 149 (14). Art. No. 144101. ISSN 0021-9606. doi:10.1063/1.5050533.

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Projection-based embedding offers a simple framework for embedding correlated wavefunction methods in density functional theory. Partitioning between the correlated wavefunction and density functional subsystems is performed in the space of localized molecular orbitals. However, during a large geometry change—such as a chemical reaction—the nature of these localized molecular orbitals, as well as their partitioning into the two subsystems, can change dramatically. This can lead to unphysical cusps and even discontinuities in the potential energy surface. In this work, we present an even-handed framework for localized orbital partitioning that ensures consistent subsystems across a set of molecular geometries. We illustrate this problem and the even-handed solution with a simple example of an S_N2 reaction. Applications to a nitrogen umbrella flip in a cobalt-based CO_2 reduction catalyst and to the binding of CO to Cu clusters are presented. In both cases, we find that even-handed partitioning enables chemically accurate embedding with modestly sized embedded regions for systems in which previous partitioning strategies are problematic.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Welborn, Matthew0000-0001-8659-6535
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2018 AIP Publishing. (Received 31 July 2018; accepted 7 September 2018; published online 8 October 2018) We thank Feizhi Ding and Sebastian Lee for helpful discussions. M.W. thanks the Resnick Sustainability Institute for a postdoctoral fellowship. T.F.M. acknowledges support in part from the NSF under Award No. CHE-1611581; additionally, 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 No. DE-SC0004993. F.R.M. is grateful for funding from EPSRC (Grant No. EP/M013111/1).
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Engineering and Physical Sciences Research Council (EPSRC)EP/M013111/1
Issue or Number:14
Record Number:CaltechAUTHORS:20181008-145630347
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90162
Deposited By: George Porter
Deposited On:08 Oct 2018 22:12
Last Modified:16 Nov 2021 00:41

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