O. V. Sizova

INDO parameters for the elements of the I and II transition rows

It is shown that with the use of published one‐center INDO parameters for transition metals M, it is not possible to reproduce experimental relative energies of the electronic states of M, M+, and M2+ accurately enough. Two new sets of INDO parameters for the elements of the I and II transition rows are developed. These parameters are obtained by the method which ensures that the calculated energy differences between atomic electron states are in agreement with the experimental data. The results of some molecular test calculations are presented.

Quantum-chemical study of donor-acceptor interactions in rhodium(I) carbonyl carboxylate complexes with phosphine ligands

The DFT B3LYP method was used to optimize the geometries, calculate the IR spectra, and analyze the electronic structures of carbonyl(carboxylato)(phosphine)rhodium(I) complexes, namely, trans-[Rh(Cl)(CO)(PPh3)2], trans-[Rh(OCOR)(CO)(PPh3)2] (R = H, CH3, and CF3), and trans-[Rh(OCOH)(CO)(PX3)2], and free PX3 molecules (X = H, F, CH3, i-Pr, Cy, and Ph). A linear correlation between v(CO) in the IR spectra of trans-[Rh(OCOH)(CO)(PX3)2] and the HOMO energy of the free PX3 molecule was found for phosphines with nonaromatic substituents X. It was concluded that the electronic state of the CO group is mainly determined by the σ-donor properties of phosphines. The distinctive features of the electronic structure of triphenylphosphine are discussed.

Electronic structure and spectra of rhodium(II) tetracarboxylate complexes

The DFT B3LYP geometry optimization was carried out and the IR spectra were calculated for rhodium(II) tetracarboxylate complexes Rh2(O2CR)4 (R = H, CH3, CF3, C6H5) and for the compound Rh2(O2CH)4(H2O)2 with two axially coordinated water molecules. A minor influence of the substituent R on the electronic structure and geometric and spectral characteristics of the cage was noted. From the calculation results, it was concluded that the Rh(II)-Rh(II) stretching vibrations should be attributed to about 300 cm−1. The results obtained for rhodium(II) dimers were compared with analogous data for Mo2(O2CH)4. Analysis of the electronic structure including consideration of the natural bond orbitals indicates the presence of a strong Rh(II)-Rh(II) single bond and a quadruple Mo(IV)-Mo(IV) bond. The electronic spectra of Rh2(O2CR)4 (R = H, C6H5) and Rh2(O2CH)4(H2O)2 were simulated by the TDDFT technique.

Quantum-chemical study of trans influence in gold(I) linear complexes

AbstractTheoretical study of trans influence of ligands in Au(I) and Ag(I) complexes is based on quantumchemical calculations fulfilled within the limits of density functional theory. Metal-ligand bond orders and their σ- and π-components were analyzed for several series of [L-M(I)-X]q complexes; the participation of s, p, and d metal orbitals in binding was characterized. The π dative interactions metal→ ligand in Ag(I) and Au(I) complexes are weakened, and trans influence is caused by a competition of σ-donor ligands for the electronic density transfer from lone pairs of ligands onto

A METHOD FOR CALCULATIONS OF THE ELECTRONIC SPECTRA OF TRANSITION METAL COMPOUNDS

0.9s + 0.4d_{z^2 }

DFT study of metastable linkage isomers of six-coordinate ruthenium nitrosyl complexes

hybrid orbitals of gold.

Chemistry of Ruthenium Polypyridine Complexes: IV. Quantum-Chemical Simulation of the Effect of Solvation Shell on the Electronic Structure of Ru(II) Complexes with Nitrogen-containing Ligands

The ab initio and semi-empirical configuration interaction wave functions of ruthenium complexes [RuL5(XY) q (L & = NH3, Cl−, CN−, XY &= N2, CO) are presented in the form of linear combinations of the valence bond (VB) structures, each structure being referred to some covalent or ionic model of the bonding in the M-XY group. The results of this VB analysis showed that [RuL5(NO)] q complexes can be described as compounds of Ru(III) and neutral NO0 with a covalent π-bond in addition to the usual coordination bond.

Quantum-chemical study of donor-acceptor interactions in chelate dicarbonyl complexes of rhodium(I)

Abstract A new method for the calculations of the electronic structure and spectra of transition metal compounds is based on the CI approach with restrictions imposed on the occupancies of the groups of molecular orbitals. Proper selection of the active space composition allows account of correlation and orbital relaxation effects with the use of a CI matrix of moderate size. A new parametrization scheme for the atomic INDO parameters for transition elements is proposed. Solvent effects are treated in the framework of a simple parametric scheme.