Computational convergence of electronic structure calculations of transition metal ligand complexes

✍ Scribed by Eric Magnusson; Nigel W. Moriarty

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 875 KB
• Volume: 14
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540140811

✦ Synopsis

Calculations of binding energies and optimum geometries of compounds of the series M(H,O) + with M = Sc to Zn have been carried out and compared with gas-phase experimental data and with the Rosi and Bauschlicher MCPF calculations. Hartree-Fock calculations and correlated calculations at MP2, MP4, and QCISD(T) levels were used to test the dependence of the results upon the level of correlation. A test of basis set dependence was also carried out, using parallel calculations on four basis sets ranging in size from a small DZ set to a TZ contraction. Correlation levels above MP2 and elaboration of the metal d-function basis set to (4di3d) size or greater were both necessary for convergence with the most uniformly reliable results obtained from QCISD(T) calculations on a basis set with a (6d/4d) contraction for the d-function space.

However, MP2 or higher-level calculations with a contracted four or five d function set [(5d/3d) or (4d/3d)] are capable of yielding results on binding energies and geometries close to the current gas-phase experimental uncertainty on electrostatically bound transition metal complexes.