A Caltech Library Service

Accurate and systematically improvable density functional theory embedding for correlated wavefunctions

Goodpaster, Jason D. and Barnes, Taylor A. and Manby, Frederick R. and Miller, Thomas F., III (2014) Accurate and systematically improvable density functional theory embedding for correlated wavefunctions. Journal of Chemical Physics, 140 (18). Art. No. 18A507. ISSN 0021-9606. doi:10.1063/1.4864040.

PDF - Published Version
See Usage Policy.


Use this Persistent URL to link to this item:


We analyze the sources of error in quantum embedding calculations in which an active subsystem is treated using wavefunction methods, and the remainder using density functional theory. We show that the embedding potential felt by the electrons in the active subsystem makes only a small contribution to the error of the method, whereas the error in the nonadditive exchange-correlation energy dominates. We test an MP2 correction for this term and demonstrate that the corrected embedding scheme accurately reproduces wavefunction calculations for a series of chemical reactions. Our projector-based embedding method uses localized occupied orbitals to partition the system; as with other local correlation methods, abrupt changes in the character of the localized orbitals along a reaction coordinate can lead to discontinuities in the embedded energy, but we show that these discontinuities are small and can be systematically reduced by increasing the size of the active region. Convergence of reaction energies with respect to the size of the active subsystem is shown to be rapid for all cases where the density functional treatment is able to capture the polarization of the environment, even in conjugated systems, and even when the partition cuts across a double bond.

Item Type:Article
Related URLs:
URLURL TypeDescription
Goodpaster, Jason D.0000-0001-6461-4501
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2014 AIP Publishing LLC. Received 21 December 2013; accepted 22 January 2014; published online 10 February 2014. This work is supported by the U. S. Army Research Laboratory and the U. S. Army Research Office (USARO) under Grant No. W911NF-10-1-0202 (J.D.G.), by the Air Force Office of Scientific Research (USAFOSR) under Grant No. FA9550-11-1-0288 (T.A.B.), and by the (U.S.) Department of Energy (DOE) under Grant No. DE-SC0006598 (J.D.G.). T.F.M. acknowledges support from a Camille and Henry Dreyfus Foundation Teacher-Scholar Award and an Alfred P. Sloan Foundation Research Fellowship. F.R.M. was visiting Caltech while most of the research was performed. He gratefully acknowledges support for the sabbatical through a University Research Fellowship from the Institute of Advanced Studies at the University of Bristol and a Royal Society Wolfson Research Merit Award.
Funding AgencyGrant Number
Army Research LaboratoryUNSPECIFIED
Army Research Office (ARO)W911NF-10-1-0202
Air Force Office of Scientific Research (AFOSR)FA9550-11-1-0288
Department of Energy (DOE)DE-SC0006598
Camille and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
University of BristolUNSPECIFIED
Issue or Number:18
Record Number:CaltechAUTHORS:20140401-104003729
Persistent URL:
Official Citation:Goodpaster, J. D., Barnes, T. A., Manby, F. R., & Miller, T. F. (2014). Accurate and systematically improvable density functional theory embedding for correlated wavefunctions. The Journal of Chemical Physics, 140(18), -. doi: doi:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:44572
Deposited By: Jason Perez
Deposited On:02 Apr 2014 14:26
Last Modified:10 Nov 2021 16:53

Repository Staff Only: item control page