*Chemistry ; 21(2): 763-9, 2015 Jan 07.*

##### RESUMO

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed-valence polyoxometalate (POM) [GeV14 O40 ](8-) (in short V14 ) by using both a t-J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest-neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V14 system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.

*J Chem Theory Comput ; 6(1): 55-65, 2010 Jan 12.*

##### RESUMO

The magnetic anisotropy of the [Ni2(en)4Cl2](2+) (en = ethylenediamine) complex has been studied using wave function based computational schemes. The spin-orbit state interaction methodology provides accurate ab initio energies and wave functions that are used to interpret the anisotropy in bimetallic complexes. The extraction of the anisotropic spin Hamiltonian is performed using the effective Hamiltonian theory. This procedure which has successfully been applied to mononuclear complexes enables one to solve the weak exchange limit. It is shown that the standard coupled spin Hamiltonian only describes a part of the anisotropy of the molecule. Important higher order terms such as the biquadratic anisotropic exchange should be included in the model for an appropriate description of the anisotropy.

*J Chem Theory Comput ; 5(11): 2977-84, 2009 Nov 10.*

##### RESUMO

Monometallic Ni(II) and Co(II) complexes with large magnetic anisotropy are studied using correlated wave function based ab initio calculations. Based on the effective Hamiltonian theory, we propose a scheme to extract both the parameters of the zero-field splitting (ZFS) tensor and the magnetic anisotropy axes. Contrarily to the usual theoretical procedure of extraction, the method presented here determines the sign and the magnitude of the ZFS parameters in any circumstances. While the energy levels provide enough information to extract the ZFS parameters in Ni(II) complexes, additional information contained in the wave functions must be used to extract the ZFS parameters of Co(II) complexes. The effective Hamiltonian procedure also enables us to confirm the validity of the standard model Hamiltonian to produce the magnetic anisotropy of monometallic complexes. The calculated ZFS parameters are in good agreement with high-field, high-frequency electron paramagnetic resonance spectroscopy and frequency domain magnetic resonance spectroscopy data. A methodological analysis of the results shows that the ligand-to-metal charge transfer configurations must be introduced in the reference space to obtain quantitative agreement with the experimental estimates of the ZFS parameters.

*J Chem Phys ; 129(10): 104102, 2008 Sep 14.*

##### RESUMO

This paper analyzes the different contributions to the magnetic coupling in systems with more than one unpaired electron per center. While in S=12 spin systems the Heisenberg Hamiltonian involving only bilinear exchange interactions is reliable for the description of the magnetic states, biquadratic exchange interactions must be sometimes introduced for S=1 (or higher) spin systems to account for isotropic deviations to Heisenberg behavior. The analysis establishes that the excited atomic states, the so-called non-Hund states, are responsible for the main contribution to the deviations. The kinetic exchange contribution and the spin, hole, and particle polarizations increase the magnetic coupling but essentially maintain the Heisenberg pattern. The importance of the different contributions has been studied for a series of Ni(2) compounds with a polarizable double azido bridge. The coupling between two Fe(3+) ions in the molecular crystal Na(3)FeS(3), which is known experimentally to present large deviations to Heisenberg behavior, has also been investigated.

*J Chem Phys ; 129(15): 154110, 2008 Oct 21.*

##### RESUMO

The variational energies of broken-symmetry single determinants are frequently used (especially in the Kohn-Sham density functional theory) to determine the magnetic coupling between open-shell metal ions in molecular complexes or periodic lattices. Most applications extract the information from the solutions of m(s)(max) and m(s)(min) eigenvalues of S(z) magnetic spin momentum, assuming that a mapping of these energies on the energies of an Ising Hamiltonian is grounded. This approach is unable to predict the possible importance of deviations from the simplest form of the Heisenberg Hamiltonians. For systems involving s=1 magnetic centers, it cannot provide an estimate of neither the biquadratic exchange integral nor the three-body operator interaction that has recently been proven to be of the same order of magnitude [Phys. Rev. B 70, 132412 (2007)]. The present work shows that one may use other broken-symmetry solutions of intermediate values of m(s) to evaluate the amplitude of these additional terms. The here-derived equations rely on the assumption that an extended Hubbard-type Hamiltonian rules the interactions between the magnetic electrons. Numerical illustrations on a model problem of two O(2) molecules and a fragment of the La(2)NiO(4) lattice are reported. The results obtained using a variable percentage of Fock exchange in the BLYP functional are compared to those provided by elaborate wave function calculations. The relevant percentage of Fock exchange is system dependent but a mean value of 30% leads to acceptable amplitudes of the effective exchange interaction.

*J Chem Phys ; 125(19): 194708, 2006 Nov 21.*

##### RESUMO

A truncated Hubbard model is developed for the description of the electronic structure of odd-electron TM-L-TM units (TM=transition metal and L=ligand). The model variationally treats both the double exchange and purely magnetic Heisenberg configurations. This Hubbard model can either be mapped on a purely magnetic Heisenber model in which the bridging oxygen is also magnetic or on a double exchange model owing to the hybridization of the magnetic and ligand or bitals. The purely magnetic Heisenberg model is analytically solved in the general case of two metals (having n magnetic orbitals) bridged by a magnetic oxygen. The comparison of the analytical expressions of the Heisenberg energies to those of the double exchange model reveals that the two model spectra are identical except for one state which does not belong to the model space of the double exchange Hamiltonian. Consequently, the fitting of the model spectra to accurate ab initio spectra does not discriminate between the physically different models. These concepts are illustrated for the Mn-O-Mn unit (or Zener polaron) found in the half-doped manganite Pr(0.6)Ca(0.4)MnO3. It is shown that in the present case the projections of the ab initio ground state wave function onto both model spaces are almost identical provided that one uses properly localized orbitals, proving that the magnetic description of the Zener polaron and the double exchange viewpoint of the electronic structure are equally valid.