Projects per year
Abstract
Embedded meanfield theory (EMFT) provides a simple, flexible framework for describing subsystems at different levels of meanfield theory. Subsystems are defined by partitioning a oneparticle 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 selfconsistent solution. To avoid this issue, we introduce subsystem partitioning of a blockorthogonalized (BO) basis set; this eliminates the unphysical collapse without significantly increasing computational cost. We also investigate a nonselfconsistent implementation of EMFT, in which the density matrix is obtained using BO partitioning and the final energy evaluated using AO partitioning; this densitycorrected 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 exactexchange 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.
Original language  English 

Pages (fromto)  16051615 
Number of pages  11 
Journal  Journal of Chemical Theory and Computation 
Volume  13 
Issue number  4 
Early online date  28 Feb 2017 
DOIs  
Publication status  Published  11 Apr 2017 
Fingerprint
Dive into the research topics of 'Embedded meanfield theory with blockorthogonalized partitioning'. Together they form a unique fingerprint.Projects
 1 Finished

Embedded meanfield theory: chemical simulation in complex environments
Manby, F. R.
1/02/15 → 31/05/18
Project: Research