A Caltech Library Service

Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes

Goodpaster, Jason D. and Barnes, Taylor A. and Manby, Frederick R. and Miller, Thomas F., III (2012) Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes. Journal of Chemical Physics, 137 (22). Art. No. 224113. ISSN 0021-9606. doi:10.1063/1.4770226.

[img] PDF - Published Version
See Usage Policy.

PDF - Submitted Version
See Usage Policy.


Use this Persistent URL to link to this item:


Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the accuracy and stability of WFT-in-DFT embedding calculations. In particular, we develop spin-dependent embedding potentials in both restricted and unrestricted orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and develop an orbital-occupation-freezing technique to improve the convergence of optimized effective potential calculations that arise in the evaluation of the embedding potential. The new techniques are demonstrated in applications to the van-der-Waals-bound ethylene-propylene dimer and to the hexa-aquairon(II) transition-metal cation. Calculation of the dissociation curve for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating errors in the dispersion interactions due to conventional exchange-correlation (XC) functionals while simultaneously avoiding errors due to subsystem partitioning across covalent bonds. Application of WFT-in-DFT embedding to the calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II) cation reveals that the majority of the dependence on the DFT XC functional can be eliminated by treating only the single transition-metal atom at the WFT level; furthermore, these calculations demonstrate the substantial effects of open-shell contributions to the embedding potential, and they suggest that restricted open-shell WFT-in-DFT embedding provides better accuracy than unrestricted open-shell WFT-in-DFT embedding due to the removal of spin contamination.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Goodpaster, Jason D.0000-0001-6461-4501
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2012 American Institute of Physics. Received 7 October 2012; accepted 23 November 2012; published online 13 December 2012. This work is supported in part by the Air Force Office of Scientific Research (FA9550-11-1-0288) and the U. S. Army Research Laboratory and the U. S. Army Research Office (W911NF-10-1-0202). T.F.M. and F.R.M. also gratefully acknowledge network funding from the NSF (CHE-1057112) and EPSRC (EP/J012742/1), respectively. Computational resources were provided by the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy (Contract No. DE-AC02-05CH11231).
Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)FA9550-11-1-0288
Army Research Office (ARO)W911NF-10-1-0202
Engineering and Physical Sciences Research Council (EPSRC)EP/J012742/1
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:22
Record Number:CaltechAUTHORS:20130123-093712451
Persistent URL:
Official Citation:Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes. Jason D. Goodpaster, Taylor A. Barnes, Frederick R. Manby, and Thomas F. Miller III. The Journal of Chemical Physics 2012 137:22
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:36528
Deposited By: Ruth Sustaita
Deposited On:23 Jan 2013 18:04
Last Modified:09 Nov 2021 23:22

Repository Staff Only: item control page