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The performance and relationship among range-separated schemes for density functional theory.
MedLine Citation:
PMID:  21861558     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
The performance and relationship among different range-separated (RS) hybrid functional schemes are examined using the Coulomb-attenuating method (CAM) with different values for the fractions of exact Hartree-Fock (HF) exchange (α), long-range HF (β), and a range-separation parameter (μ), where the cases of α + β = 1 and α + β = 0 were designated as CA and CA0, respectively. Attenuated PBE exchange-correlation functionals with α = 0.20 and μ = 0.20 (CA-PBE) and α = 0.25 and μ = 0.11 (CA0-PBE) are closely related to the LRC-ωPBEh and HSE functionals, respectively. Time-dependent density functional theory calculations were carried out for a number of classes of molecules with varying degrees of charge-transfer (CT) character to provide an assessment of the accuracy of excitation energies from the CA functionals and a number of other functionals with different exchange hole models. Functionals that provided reasonable estimates for local and short-range CT transitions were found to give large errors for long-range CT excitations. In contrast, functionals that afforded accurate long-range CT excitation energies significantly overestimated energies for short-range CT and local transitions. The effects of exchange hole models and parameters developed for RS functionals for CT excitations were analyzed in detail. The comparative analysis across compound classes provides a useful benchmark for CT excitations.
Authors:
Kiet A Nguyen; Paul N Day; Ruth Pachter
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  135     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2011 Aug 
Date Detail:
Created Date:  2011-08-24     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  074109     Citation Subset:  IM    
Affiliation:
Materials and Manufacturing Directorate, Air Force Research Laboratory, Wright-Patterson Air Force Base, Ohio 45433, USAUES, Inc., Dayton, Ohio 45432, USAGeneral Dynamics Information Technology, Inc., Dayton, Ohio 45431, USA.
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