%0 DATA
%A Ivelina, Georgieva
%A Natasha, Trendafilova
%A Adélia, J. A. Aquino
%A Hans, Lischka
%D 2007
%T Theoretical Study of Metal−Ligand Interaction in Sm(III), Eu(III), and
Tb(III) Complexes of Coumarin-3-Carboxylic Acid in the Gas Phase and
Solution
%U https://acs.figshare.com/articles/journal_contribution/Theoretical_Study_of_Metal_Ligand_Interaction_in_Sm_III_Eu_III_and_Tb_III_Complexes_of_Coumarin_3_Carboxylic_Acid_in_the_Gas_Phase_and_Solution/2969830
%R 10.1021/ic7016616.s002
%2 https://acs.figshare.com/ndownloader/files/4669075
%K energy partitioning analysis
%K continuum solvation model
%K Gas Phase
%K SolutionThe interaction
%K carboxylate moiety
%K interaction term
%K population analyses
%K interaction terms
%K ligand deformation energies
%K deprotonated form
%K Solvent effects
%K binding energies
%K covalent contributions
%K water clusters
%K CCSD
%K covalent contribution
%K Theoretical Study
%K DFT
%K reference MP 2
%K Ln
%K energy decomposition calculations
%K electron distribution analysis
%X The interaction of lanthanide(III) cations (Ln(III) = Sm(III), Eu(III), and Tb(III)) with the deprotonated form of the
coumarin-3-carboxylic acid (*cca*^{-}^{}) has been investigated by density functional theory (DFT/B3LYP) and confirmed
by reference MP2 and CCSD(T) computations. Solvent effects on the geometries and stabilities of the Ln(III)
complexes were computed using a combination of water clusters and a continuum solvation model. The following
two series of systems were considered: (i) Ln(*cca*)^{2+}, Ln(*cca*)_{2}^{+}, Ln(*cca*)_{3} and (ii) Ln(*cca*)(H_{2}O)_{2}Cl_{2}, Ln(*cca*)_{2}(H_{2}O)_{2}Cl, Ln(*cca*)_{3}. The strength and character of the Ln(III)−*cca*^{-}^{} bidentate bonding were characterized by calculated
Ln−O bond lengths, binding energies, ligand deformation energies, energy partitioning analysis, σ-donation
contributions, and natural population analyses. The energy decomposition calculations predicted predominant
electrostatic interaction terms to the Ln−*cca* bonding (ionic character) and showed variations of the orbital interaction
term (covalent contributions) for the Ln−*cca* complexes studied. Electron distribution analysis suggested that the
covalent contribution comes mainly from the interaction with the carboxylate moiety of *cca*^{-}.