Document Detail


Assessing the performance of density functional theory for the electronic structure of metal-salens: the d6-metals.
MedLine Citation:
PMID:  19621915     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
The energies and optimized geometries of the lowest lying singlet, triplet, and quintet states for the Fe(II)-, Co(III)-, Ni(IV)-, Ru(II)-, Rh(III)-, and Pd(IV)-salens have been computed with the B3LYP and BP86 density functional theory (DFT) methods, and the results are compared to more robust complete active-space self-consistent field (CASSCF) values. Density functional optimizations are performed using two different models of the salen ligand, and CASSCF relative energies at these DFT geometries show no appreciable difference whether the smaller or the larger model salen is considered. Unlike in our previous studies on the d0 and d2 metal-salens, DFT methods rarely predict the correct ordering of states compared to high-level complete active-space third-order perturbation theory (CASPT3) computations. The DFT energy gaps, moreover, are generally much smaller than those predicted by the CASPT3 method. Similarly to our previous studies, DFT optimized geometries closely match the CASSCF optimized geometries with errors mostly on the order of 0.1 A least root mean squared deviation. The electronic structure of the Co(III)- and Rh(III)-salens is particularly challenging, and significant differences between CASPT2 and CASPT3 relative energies were observed in these cases.
Authors:
Tait Takatani; John S Sears; C David Sherrill
Related Documents :
19715285 - New insight into chiroptical properties of 1,2-diols cyclic sulfites.
16351305 - On fitting a gold embedded atom method potential using the force matching method.
19475185 - Double excitation effect in non-adiabatic time-dependent density functional theory with...
25137595 - Mnii/iii complexes as promising redox mediators in quantum dot sensitized solar cells.
12241215 - Large-bandgap behavior in transport of electrons through individual dna molecules cause...
11984855 - Isomers of c(20): an energy profile.
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  113     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2009 Aug 
Date Detail:
Created Date:  2009-09-01     Completed Date:  2010-01-05     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  9231-6     Citation Subset:  -    
Affiliation:
Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Export Citation:
APA/MLA Format     Download EndNote     Download BibTex
MeSH Terms
Descriptor/Qualifier:

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


Previous Document:  Experimental detection and theoretical characterization of germanium-doped lithium clusters Li(n)Ge ...
Next Document:  Hydrolysis mechanisms for the organopalladium complex [Pd(CNN)P(OMe)3]BF4 in sulfuric acid.