Bond strength from density-functional

MacGregor SA, Neave GW, Smith C (2003) Theoretical studies on C-heteroatom bond formation via reductive elimmation from group 10 M(PH3)2(CH3)(X) species (X = CH3, NH2, OH, SH) and the determination of metal-X bond strengths using density functional theory. Faraday Discuss 124 111-127... 

In reviewing the performance of density functional theory applied to hydrogen bonded complexes of moderate strength, we repeatedly noted a systematic underestimation of the interaction energies for many types of functionals, usually below 2 kcal/mol. This has been related by some researchers to the inability of modem functionals to describe those contributions to intermolecular binding energies which stem from dispersion forces. Dispersion... 

Vibrational frequencies measured in IR experiments can be used as a probe of the metal—ligand bond strength and hence for the variation of the electronic structure due to metal—radical interactions. Theoretical estimations of the frequencies are obtained from the molecular Hessian, which can be straightforwardly calculated after a successful geometry optimization. Pure density functionals usually give accurate vibrational frequencies due to an error cancellation resulting from the neglect of... 

All the available experimental and theoretical work performed on NEMCA leads to the conclusion that electrochemical promotion is caused by electrocatalytic introduction of promoting species like O2 or Na+ from the solid electrolyte to the catalyst/gas interface where a double layer is formed, of which density and internal electric field vary with the applied potential. The latter affects the work function at the surface and therewith the bond strength of adsorbing reactants and intermediates. This causes the dramatic and reversible modification in catalytic rate (Vayenas and Koutsodontis, 2008 see Figure 28). 

Density functional calculations (X) on the strengths of multiple metal-metal bonds in binuclear complexes such as M2Cl4(PR3)4 and M2X6, where the bonding primarily involves nd-orbitals rather than (n+l)s orbitals,reveal (XX) on the other hand only modest contributions from relativistic corrections (6-10 Kcal mol ) for the 5d homologues.The calculated order of stability for the M-M... 

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