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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. Journal of Chemical Physics, 151 (6). Art. No. 064112. ISSN 0021-9606. doi:10.1063/1.5109882.

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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 (WF) method, while the remainder of the system is described at the level of density functional theory (DFT). 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 a numerical demonstration of the method for several applications, including a calculation of a minimum energy pathway for a hydride transfer in a cobalt-based molecular catalyst using the nudged-elastic-band method at the coupled-cluster single double-in-DFT level of theory, which reveals large differences from the transition state geometry predicted using DFT.

Item Type:Article
Related URLs:
URLURL TypeDescription Materials Paper
Lee, Sebastian J. R.0000-0001-7006-9378
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2019 Published under license by AIP Publishing. Submitted: 13 May 2019; Accepted: 3 July 2019; Published Online: 9 August 2019. We thank Matthew Welborn for helpful discussions. This material is based on the work supported by the U.S. Army Research Laboratory under Grant No. W911NF-12-2-0023 (S.J.R.L.). 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 from the Engineering and Physical Sciences Research Council for funding (No. EP/M013111/1).
Group:JCAP, Resnick Sustainability Institute
Funding AgencyGrant Number
Army Research Office (ARO)W911NF-12-2-0023
Resnick Sustainability InstituteUNSPECIFIED
Department of Energy (DOE)DE-FOA-0001912
Engineering and Physical Sciences Research Council (EPSRC)EP/M013111/1
Issue or Number:6
Record Number:CaltechAUTHORS:20190513-111036074
Persistent URL:
Official Citation:Analytical gradients for projection-based wavefunction-in-DFT embedding. Sebastian J. R. Lee, Feizhi Ding, Frederick R. Manby, and Thomas F. Miller III. The Journal of Chemical Physics 151:6; doi: 10.1063/1.5109882
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:16 Nov 2021 17:12

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