A complete set of fully-relativistic benchmark results for the bond lengths and vibrational frequencies of uranyl at various levels of correlation treatment are presented. It is shown that the relativistic and correlation affects are of the same magnitude and should be treated on an equal footing. Results of uranyl calculations using various relativistic effective core potentials (RECP) are presented. Appropriate choices for RECP's for use in density functional theory (DFT) calculations in the local density approximation (LDA) and with the gradient-corrected B3LYP exchange-correlation functional are discussed. The conclusion is reached that small-core RECP's need to be used and that the best results as compared to the benchmark values are obtained by using a DFT functional that includes some fraction of Hartree-Fock Exchange.
Revised: July 12, 2002 |
Published: May 1, 2002
Citation
De Jong W.A., R.J. Harrison, J.A. Nichols, and D.A. Dixon. 2002.Fully Relativistic Correlated Benchmark Results for Uranyl and a Critical Look at Relativistic Effective Core Potentials for Uranium.Theoretical Chemistry Accounts 107, no. 5:318.PNNL-SA-34493.