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Performance of the Harris functional for extended basis sets at the Hartree–Fock and density functional levels
Author(s) -
Cullen John
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10406
Subject(s) - energy functional , density functional theory , basis set , hybrid functional , basis (linear algebra) , hartree–fock method , kohn–sham equations , open shell , orbital free density functional theory , hartree , polarization (electrochemistry) , computational chemistry , quantum mechanics , chemistry , statistical physics , physics , mathematics , geometry
The Harris functional is a noniterative variational procedure that uses an input charge density to produce an energy that is surprisingly accurate compared to the converged Kohn–Sham self‐consistent result. We adapted and generalized this functional for the Hartree–Fock closed‐ and open‐shell cases as well as examined its use for hybrid density functional methods such as B3LYP. Analysis of extended basis set calculations shows that at the B3LYP level an input density formed from a double zeta + polarization orbital basis is accurate enough to reproduce the energy of triple zeta + double polarization + diffuse orbital basis. For large molecules this translates into a computational speed that can be an order of magnitude faster. In the case of Hartree–Fock calculations a “bootstrapping technique” that employs successive applications of the Harris functional can further reduce computational times while retaining sufficient accuracy. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 637–648, 2004