Published September 1, 2017
| public
Journal Article
Density-based errors in mixed-basis mean-field electronic structure, with implications for embedding and QM/MM methods
Chicago
Abstract
We consider mean-field electronic structure calculations with subsystems that employ different atomic-orbital basis sets. A major source of error arises in charge-manifestation reactions (including ionization, electron attachment, or deprotonation) due to electronic density artifacts at the subsystem interface. The underlying errors in the electronic density can be largely eliminated with Fock-matrix corrections or by avoiding the use of a minimal basis set in the low-level region. These corrections succeed by balancing the electronegativity of atoms at the subsystem interface, much as link-atoms in QM/MM calculations rely upon balancing the electronegativity of atoms in the truncated QM region.
Additional Information
© 2017 Published by Elsevier B.V. Received 28 February 2017, Accepted 18 April 2017, Available online 19 April 2017. 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 DE-SC0004993. The work was also supported by the U.S. Army Research Laboratory under Grant No. W911NF-12-2-0023. S.J.R.L. acknowledges a fellowship from the Caltech Resnick Institute, K.M. acknowledges financial support for his PhD research from Toyota Central R&D Labs, Inc., F.R.M. is grateful for financial support from the Engineering and Physical Sciences Research Council (EP/M013111/1), and T.F.M. acknowledges support from a Camille Dreyfus Teacher-Scholar Award.Additional details
- Eprint ID
- 77248
- Resolver ID
- CaltechAUTHORS:20170508-080116014
- Department of Energy (DOE)
- DE-SC0004993
- Army Research Office (ARO)
- W911NF-12-2-0023
- Resnick Sustainability Institute
- Toyota Central R&D Labs, Inc.
- Engineering and Physical Sciences Research Council (EPSRC)
- EP/M013111/1
- Camille and Henry Dreyfus Foundation
- Created
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2017-05-08Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute