Monoligand Zn(II) Complexes: Ab Initio Benchmark Calculations and Comparison with Density Functional Theory Methodologies
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- 作者：Ví ; ctor M. Rayó ; n ; Haydee Valdé ; s ; Natalia Dí ; az ; Dimas Suá ; rez
- 刊名：Journal of Chemical Theory and Computation
- 出版年：2008
- 出版时间：February 2008
- 年：2008
- 卷：4
- 期：2
- 页码：243 - 256
- 全文大小：286K
- 年卷期：v.4,no.2(February 2008)
- ISSN：1549-9626
文摘
A systematic theoretical study on several models of Zn(II) complexes has been carriedout employing both ab initio correlated wave function and density functional methods. Theperformance of five different functionals namely PW91, PBE, B3LYP, MPWLYP1M, and TPSSin the prediction of metal-ligand bond distances, binding energies, and proton affinities hasbeen assessed comparing the results to those obtained with the MP2 and CCSD(T) wave functionmethodologies. Several basis sets ranging from double-
up to quintuple- quality have beenused, including the recently developed all-electron correlation consistent basis sets for zinc. Itis shown that all the tested functionals overestimate both the metal-ligand bond distances andthe binding energies, being that the B3LYP and TPSS functionals are the ones that perform thebest. An analysis of the metal-ligand interaction energy shows that induction and charge-transfereffects play a prominent role in the bonding of these systems, even for those complexes withthe less polarizable ligands. This finding highlights the importance of a correct description ofthe polarization of the monomers' charge densities by any theoretical method which aims to beapplied to the study of Zn(II) complexes.
up to quintuple- quality have beenused, including the recently developed all-electron correlation consistent basis sets for zinc. Itis shown that all the tested functionals overestimate both the metal-ligand bond distances andthe binding energies, being that the B3LYP and TPSS functionals are the ones that perform thebest. An analysis of the metal-ligand interaction energy shows that induction and charge-transfereffects play a prominent role in the bonding of these systems, even for those complexes withthe less polarizable ligands. This finding highlights the importance of a correct description ofthe polarization of the monomers' charge densities by any theoretical method which aims to beapplied to the study of Zn(II) complexes.