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Accurate basis set truncation for wavefunction embedding

Barnes, Taylor A. and Goodpaster, Jason D. and Manby, Frederick R. and Miller, Thomas F., III (2013) Accurate basis set truncation for wavefunction embedding. Journal of Chemical Physics, 139 (2). Art. No. 024103. ISSN 0021-9606. doi:10.1063/1.4811112.

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Density functional theory (DFT) provides a formally exact framework for performing embedded subsystem electronic structure calculations, including DFT-in-DFT and wavefunction theory-in-DFT descriptions. In the interest of efficiency, it is desirable to truncate the atomic orbital basis set in which the subsystem calculation is performed, thus avoiding high-order scaling with respect to the size of the MO virtual space. In this study, we extend a recently introduced projection-based embedding method [F. R. Manby, M. Stella, J. D. Goodpaster, and T. F. Miller III, J. Chem. Theory Comput. 8, 2564 (2012)]10.1021/ct300544e to allow for the systematic and accurate truncation of the embedded subsystem basis set. The approach is applied to both covalently and non-covalently bound test cases, including water clusters and polypeptide chains, and it is demonstrated that errors associated with basis set truncation are controllable to well within chemical accuracy. Furthermore, we show that this approach allows for switching between accurate projection-based embedding and DFT embedding with approximate kinetic energy (KE) functionals; in this sense, the approach provides a means of systematically improving upon the use of approximate KE functionals in DFT embedding.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Goodpaster, Jason D.0000-0001-6461-4501
Manby, Frederick R.0000-0001-7611-714X
Miller, Thomas F., III0000-0002-1882-5380
Additional Information:© 2013 AIP Publishing LLC. Received 14 April 2013; accepted 31 May 2013; published online 8 July 2013. 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, by the Air Force Office of Scientific Research (USAFOSR) under Grant No. FA9550-11-1-0288, and by the Office of Naval Research (ONR) under Grant No. N00014-10-1-0884. T.A.B. acknowledges support from a National Defense Science and Engineering Graduate Fellowship, and T.F.M. acknowledges support from a Camille and Henry Dreyfus Foundation New Faculty Award and an Alfred P. Sloan Foundation Research Fellowship.
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
Office of Naval Research (ONR)N00014-10-1-0884
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Subject Keywords:density functional theory, molecular clusters, orbital calculations, polymers, water, wave functions
Issue or Number:2
Classification Code:PACS: 31.15.E-; 36.20.Kd; 36.40.Cg
Record Number:CaltechAUTHORS:20130826-111810684
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40923
Deposited By: Tony Diaz
Deposited On:26 Aug 2013 19:58
Last Modified:10 Nov 2021 04:24

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