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Analytical Gradients for Projection-Based Wavefunction-in-DFT Embedding

Lee, Sebastian J. R. and Ding, Feizhi and Manby, Frederick R. and Miller, Thomas F., III (2019) Analytical Gradients for Projection-Based Wavefunction-in-DFT Embedding. . (Unpublished)

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Projection-based embedding provides a simple, robust, and accurate approach for describing a small part of a chemical system at the level of a correlated wavefunction method while the remainder of the system is described at the level of density functional theory. Here, we present the derivation, implementation, and numerical demonstration of analytical nuclear gradients for projection-based wavefunction-in-density functional theory (WF-in-DFT) embedding. The gradients are formulated in the Lagrangian framework to enforce orthogonality, localization, and Brillouin constraints on the molecular orbitals. An important aspect of the gradient theory is that WF contributions to the total WF-in-DFT gradient can be simply evaluated using existing WF gradient implementations without modification. Another simplifying aspect is that Kohn-Sham (KS) DFT contributions to the projection-based embedding gradient do not require knowledge of the WF calculation beyond the relaxed WF density. Projection-based WF-in-DFT embedding gradients are thus easily generalized to any combination of WF and KS-DFT methods. We provide numerical demonstration of the method for benchmark systems, including calculation of a minimum energy pathway for intramolecular hydrogen-atom transfer reaction in malondialdehyde using the nudged-elastic-band method at the CCSD-in-DFT level of theory.

Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription Paper
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:This material is based upon work supported by the U.S. Army Research Laboratory under Grant No. W911NF-12-2-0023 (S.J.R.L.); 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 Number desc0004993 (F.D.). S.J.R.L. thanks the Caltech Resnick Sustainability Institute for a graduate fellowship. T.F.M. and F.R.M. acknowledge joint support from the DOE (Award No. DEFOA-0001912), and F.R.M. acknowledges support form the Engineering and Physical Sciences Research Council for funding (EP/M013111/1).
Group:JCAP, Resnick Sustainability Institute
Funding AgencyGrant Number
Army Research Office (ARO)W911NF-12-2-0023
Department of Energy (DOE)DE-SC0004993
Resnick Sustainability InstituteUNSPECIFIED
Department of Energy (DOE)DE-FOA-0001912
Engineering and Physical Sciences Research Council (EPSRC)EP/M013111/1
Record Number:CaltechAUTHORS:20190513-111036074
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:95433
Deposited By: Tony Diaz
Deposited On:13 May 2019 18:30
Last Modified:13 May 2019 18:30

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