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Correcting density-driven errors in projection-based embedding

Pennifold, Robert C. R. and Bennie, Simon J. and Miller, Thomas F., III and Manby, Frederick R. (2017) Correcting density-driven errors in projection-based embedding. Journal of Chemical Physics, 146 (8). Art. No. 084113. ISSN 0021-9606. doi:10.1063/1.4974929.

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Projection-based embedding provides a simple and numerically robust framework for multiscale wavefunction-in-density-functional-theory (WF-in-DFT) calculations. The approach works well when the approximate DFT is sufficiently accurate to describe the energetics of the low-level subsystem and the coupling between subsystems. It is also necessary that the low-level DFT produces a qualitatively reasonable description of the total density, and in this work, we study model systems where delocalization error prevents this from being the case. We find substantial errors in embedding calculations on open-shell doublet systems in which self-interaction errors cause spurious delocalization of the singly occupied orbital. We propose a solution to this error by evaluating the DFT energy using a more accurate self-consistent density, such as that of Hartree-Fock (HF) theory. These so-called WF-in-(HF-DFT) calculations show excellent convergence towards full-system wavefunction calculations.

Item Type:Article
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URLURL TypeDescription
Miller, Thomas F., III0000-0002-1882-5380
Manby, Frederick R.0000-0001-7611-714X
Additional Information:© 2017 AIP Publishing LLC. All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license ( (Received 20 October 2016; accepted 13 January 2017; published online 28 February 2017) We are grateful to EPSRC for funding: RCRP is supported through the Doctoral Training Grant, S.J.B. through EP/K018965/1, EP/M022129/1, and the BBSRC through BB/L018756/1. T.F.M. acknowledges support from the National Science Foundation (NSF) CAREER Award under Grant No. CHE-1057112 and from the U.S. Army Research Laboratory under Grant No. W911NF-12-2-0023. All data produced in this work are available in an open-access repository.
Funding AgencyGrant Number
Engineering and Physical Sciences Research Council (EPSRC)EP/K018965/1
Engineering and Physical Sciences Research Council (EPSRC)EP/M022129/1
Biotechnology and Biological Sciences Research Council (BBSRC)BB/L018756/1
Army Research Office (ARO)W911NF-12-2-0023
Issue or Number:8
Record Number:CaltechAUTHORS:20170228-160004168
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74610
Deposited By: George Porter
Deposited On:01 Mar 2017 16:17
Last Modified:11 Nov 2021 05:28

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