Theoretical studies of the first- and second-row transition-metal methyls and their positive ions

Abstract

Theoretical studies of the first and secondrow transitionmetal mono and dicarbonyl positive ions J. Chem. Phys. 93, 609 (1990); 10.1063/1.459508 Positive ions of the first and secondrow transition metal hydrides J. Chem. Phys. 87, 481 (1987); 10.1063/1.453594Theoretical spectroscopic parameters for the lowlying states of the secondrow transition metal hydridesThe metal-carbon bond dissociation energies (Do) and geometries for the first-and secondrow transition-metal methyl neutrals and positive ions are determined. The computed Do values for the positive ions compare favorably with experiment, except for RuCH3+ , RhCH 3 + , and PdCH 3 + where the experimental values are 10--15 kcallmollarger. The computed Do values for the hydride and methyl positive ions are similar for all metals in both transition rows except for Cu and Ag. However, for the neutral systems the Do values for the methyls are smaller, especially on the right-hand side of both transition rows where the differences approach 15 kcallmol. In general, the dissociation energies do not follow simple trends, as the individual Do values are significantly affected by the relative spacings between the atomic states of the metal. The study of all of the methyl neutral and ions of both transition rows presented here provides a consistent set of data for the dissociation energies, thereby allowing a critical assessment of the experimental data for these molecular species, and an enhanced understanding of the different bonding mechanisms.

Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations

“…6-31+G** basis set were used for the light elements and for the Co we used the Wachters basis set with f functions. [5,6] For some cases, we included solvation effects using the SWIG C-PCM approach (CH 3 CN, = 35.9, ∞ = 1.8, r 0 = 2.18 from UFF). [7,8] For this cases, free energies are calculated as:…”

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

“…In contrast, the CCVB wave function for this case is built from only 21 parameters. We have included CASSCF and UHF results, and all calculations used the Wachters+f basis set [237][238][239]. The energies are relative to two times the septet-spin Cr energy.…”

Comparison of density functionals for energy and structural differences between the high- [5T2g:(t2g)4(eg)2] and low- [1A1g:(t2g)6(eg)] spin states of iron(II) coordination compounds. II. More functionals and the hexaminoferrous cation, [Fe(NH3)6]2+

“…͓Basis sets were obtained from the file transfer protocol ͑ftp͒ server of the quantum chemistry group at the University of Karlsruhe ͑Germany͒ under ftp:// ftp.chemie.uni-karlsruhe.de/pub/basen͔. The metal in Basis C is described by the Wachters basis 53 with two sets of p-type polarization functions and three f -sets contracted in a 2,1 fashion by Bauschlicher et al 54 (14s11p6d3 f contracted to 8s6 p4d2 f ; 62111111/331211/3111/21͒. The second basis set ͑Basis D, 423 functions͒ is more extensive and features a second set of p-polarization functions on H and an additional f -set for N ͑TZVPP͒ basis.…”