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Quantum Chemistry of FLPs and Their Activation of Small Molecules: Methodological Aspects.
MedLine Citation:
PMID:  23277381     Owner:  NLM     Status:  Publisher    
We discuss methodological aspects of the computation of structures and energies of three common FLPs which are able to activate dihydrogen under ambient conditions. The effect of London dispersion corrections by the DFT-D3 scheme and solvent as well as rovibrational corrections to yield free reaction enthalpies in solutions are described. Common density functionals of semi-local, hybrid, and double-hybrid type as well as (SCS-)MP2 wave function based methods with very large AO basis sets are investigated. It is found that reliable structures (in comparison to X-ray data) are already obtained using relatively cheap DFT methods like TPSS-D3/TZ. The variations between different density functionals for electronic reaction energies are small to moderate (1-2 kcal/mol which is about 10% of the H(2) was addition energy). Dispersion corrections are found to be essential for accurate thermochemistry. Computed free H(2) reaction enthalpies in the gas phase are close to zero while values computed in common solvents with the COSMO-RS continuum solvation model are strongly exergonic (about -10 kcal/mol in CH(2)Cl(2)). This new finding emphasizes the important role of the solvent for FLP chemistry involving zwitterionic species. According to our results the future for reliable quantum chemistry of FLP processes is bright.
Birgitta Schirmer; Stefan Grimme
Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2013-1-1
Journal Detail:
Title:  Topics in current chemistry     Volume:  -     ISSN:  0340-1022     ISO Abbreviation:  Top Curr Chem     Publication Date:  2013 Jan 
Date Detail:
Created Date:  2013-1-1     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0432204     Medline TA:  Top Curr Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstr 40, 48153, Münster, Germany.
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