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...

Using density functional theory (DFT) with the PBE0 density functional we investigated the role of surface dopants in the molecular and dissociative adsorption of O2 onto Al clusters of types Al50, Al50Alad, Al50X and Al49X, where X represents a dopant atom of the following elements Si, Mg, Cu, Sc, Zr, and Ti. Each dopant atom was placed on the Al(111) surface as an adatom or as a substitutiona...

Abstract In this work, we systematically evaluate the accuracy in band gap prediction of range-separated hybrid functionals on a large set semiconducting and insulating materials carry out comparisons with performance their global counterparts. We observe that all correctly describe long-range dielectric screening significantly improve upon standard such as PBE0 HSE06. The choice short-range Fo...

Abstract Fine tuning and microscopic control of van der Waals interactions through oriented external electric fields (OEEF) mandates an accurate systematic understanding intermolecular response properties. Having taken exploratory steps into this direction, we present a study interaction induced dipole properties all molecular dimers in the S66 set, relying on CCSD(T)-F12b/aug-cc-pVDZ-F12 as re...

Transmetalation is a key elementary reaction of many important catalytic reactions. Among these, 1,4-addition of arylboronic acids to organic acceptors such as α,β-unsaturated ketones has emerged as one of the most important methods for asymmetric C-C bond formation. A key intermediate for the B-to-Rh transfer arising from quaternization on a boronic acid by a Rh-bound hydroxide (the active cat...