Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published April 11, 2017 | Supplemental Material
Journal Article Open

Embedded Mean-Field Theory with Block-Orthogonalized Partitioning

Abstract

Embedded mean-field theory (EMFT) provides a simple, flexible framework for describing subsystems at different levels of mean-field theory. Subsystems are defined by partitioning a one-particle basis set, with a natural choice being the atomic orbital (AO) basis. Although generally well behaved, EMFT with AO partitioning can exhibit unphysical collapse of the self-consistent solution. To avoid this issue, we introduce subsystem partitioning of a block-orthogonalized (BO) basis set; this eliminates the unphysical collapse without significantly increasing computational cost. We also investigate a non-self-consistent implementation of EMFT, in which the density matrix is obtained using BO partitioning and the final energy evaluated using AO partitioning; this density-corrected EMFT approach is found to yield more accurate energies than BO partitioning while also avoiding issues of the unphysical collapse. Using these refined implementations of EMFT, previously proposed descriptions of the exact-exchange coupling between subsystems are compared: although the EX1 coupling scheme is slightly more accurate than EX0, the small improvement does not merit its substantially greater computational cost.

Additional Information

© 2017 American Chemical Society. Received 1 November 2016. Published online 28 February 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. Additionally, T.F.M. acknowledges support from a Camille Dreyfus Teacher-Scholar Award, and F.R.M. acknowledges funding from EPSRC (EP/M013111/1). The authors declare no competing financial interest.

Attached Files

Supplemental Material - ct6b01065_si_001.pdf

Files

ct6b01065_si_001.pdf
Files (855.0 kB)
Name Size Download all
md5:f4f48b869ee892784f8b934adfafe58a
855.0 kB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 25, 2023