Theoretical Estimation of Vibrational Frequencies Involving Transition Metal Compounds

Abstract

The reliability of effective core potentials (ECPs) for estimating vibrational frequencies of transition metal (TM) complexes is assessed in relation to all-electron methods for main group compounds. Complexes with a multiple bond between a transition metal and chalcogen (O, S, or Se), chalcogenides, are investigated using the Stevens ECP/valence basis set scheme. Statistical treatment of the data indicates that ECPs, in addition to reliably modeling electronic structure, can be successful in estimating vibrational frequencies for TM complexes. As expected, theoretical prediction of vibrational data is not as accurate as the prediction of metric data for chalcogenides. However, agreement with experiment is still very good at the Hartree-Fock level of theory and is in even better accord upon the use of simple corrections to model well-known computational deficiencies (e.g., the neglect of anharmonic effects). Analysis of the data show interesting differences in predictive ability for first row transition metals versus second-and third-row analogues and oxo complexes versus their congeners with heavier chalcogens.

meso-N-Methylation of a porphyrinoid complex: activating the H-atom transfer capability of an inert ReV(O) corrolazine

“…These structures led to calculated values of ν(Re–O) = 1054 cm −1 for the parent compound and 1063 cm −1 for 1 . Although these vibrational frequencies are larger than the experimental data, 13 the difference between the calculated ν(Re–O) values for 1 and the parent complex is Δν(Re–O)) = 9 cm −1 , in excellent agreement with experiment.…”

Rhenium(v)–oxo corrolazines: isolating redox-active ligand reactivity

“…DFT is known to overestimate vibrational frequencies due to systematic errors. 16 However, the difference between the calculated v(Re-O) values for 2 and 3 (Dv(ReO) = 9 cm À1 ) is in excellent agreement with experiment (11 cm À1 ).…”

Soluble Guanylate Cyclase Is Activated Differently by Excess NO and by YC-1: Resonance Raman Spectroscopic Evidence

“…The former value is in the range generally found with BLYP functional for bonds between first-row atoms (40). For metal-ligand bonds, scaling factors have not been systematically analyzed, although in a Hartree-Fock study of metal-oxo stretches a scaling factor of 0.86 was obtained for first row transition metals (41). …”