The role of various factors (structure, solvent, and relativistic treatment) was evaluated for square-planar 4d and 5d transition-metal complexes. The DFT method for calculating the structures was calibrated using a cluster approach and compared to X-ray geometries, with the PBE0 functional (def2-TZVPP basis set) providing the best results, followed closely by the hybrid TPSSH and the MN12SX fu...

The reaction of [RuCl2(CO)3]2 and Te2Tpn2 (Tpn=thiophen-2-yl, C4H3S) in the absence light resulted formation cct-[RuCl2(CO)2(TeTpn2)2] (1) [cis(Cl)-cis(CO)-trans(TeTpn2)] TeTpn2 (2) together with precipitation tellurium. complex 1 monotelluride 2 were characterized by NMR spectroscopy single-crystal X-ray diffraction. decomposition to has been monitored 125Te seemed be faster than ligand substi...

A new, parametrized many-body tight-binding model is proposed for calculating the potential energy surface for aluminum nanoparticles. The parameters have been fitted to reproduce the energies for a variety of aluminum clusters sAl2, Al3, Al4, Al7, Al13d calculated recently by the PBE0/MG3 method as well as the experimental face-centered-cubic cohesive energy, lattice constant, and a small set ...

The performance of the M06 family of exchange-correlation potentials for describing the electronic structure and the Heisenberg magnetic coupling constant (J) is investigated using a set of representative open-shell systems involving two unpaired electrons. The set of molecular systems studied has well defined structures, and their magnetic coupling values are known experimentally. As a general...

Imposition of the constraint that, for the hydrogen atom, the exchange energy cancels the Coulomb repulsion energy yields a non-empirical re-parameterization of the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) exchange-correlation energy functional, and of the related PBE hybrid (PBE0). The re-parameterization, which leads to an increase of the gradient contribution to ...

Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology...

The performance of 23 density functionals, including one LDA, four GGAs, three meta-GGAs, three hybrid GGAs, eight hybrid meta-GGAs, and ten double-hybrid functionals, was investigated for the computation of activation energies of various covalent main-group single bonds by four catalysts: Pd, PdCl(-), PdCl2, and Ni (all in the singlet state). A reactant complex, the barrier, and reaction energ...