Absence of collective effects in Heisenberg systems with localized magnetic moments

Existence of collective effects in magnetic coupling in ionic solids is studied by mapping spin eigenstates of the Heisenberg and exact nonrelativistic Hamiltonians on cluster models representing KNiF3, K2NiF4, NiO, and La2CuO4. Ab initio techniques are used to estimate the Heisenberg constant J. For clusters with two magnetic centers, the values obtained are about the same for models having more magnetic centers. The absence of collective effects in J strongly suggests that magnetic interactions in this kind of ionic solids are genuinely local and entangle only the two magnetic centers involved.

MgO/Ag(001) interface structure and STM images from first principles

The interface of MgO/Ag(001) has been studied with density functional theory applied to slabs. We have found that regular MgO films show a small adhesion to the silver substrate, the binding can be increased in off-stoichiometric regimes, either by the presence of O vacancies at the oxide film or by a small excess of O atoms at the interface between the ceramic to the metal. By means of theoretical methods, the scanning tunneling microscopy signatures of these films is also analyzed in some detail. For defect free deposits containing 1 or 2 ML and at low voltages, tunnelling takes place from the surface Ag substrate, and at large positive voltages Mg atoms are imaged. If defects, oxygen vacancies, are present on the surface of the oxide they introduce much easier channels for tunnelling resulting in big protrusions and controlling the shape of the image, the extra O stored at the interface can also be detected for very thin films.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Nuclear incompressibility in the quasilocal density functional theory

We explore the ability of the recently established quasilocal density functional theory for describing the isoscalar giant monopole resonance. Within this theory we use the scaling approach and perform constrained calculations for obtaining the cubic and inverse energy weighted moments (sum rules) of the RPA strength. The meaning of the sum rule approach in this case is discussed. Numerical calculations are carried out using Gogny forces and an excellent agreement is found with HF+RPA results previously reported in literature. The nuclear matter compression modulus predicted in our model lies in the range 210230 MeV which agrees with earlier findings. The information provided by the sum rule approach in the case of nuclei near the neutron drip line is also discussed.

Theory for the Photoacoustic Response to X-Ray Absorption

A microscopic theory is presented for the photoacoustic effect induced in solids by x-ray absorption. The photoacoustic effect results from the thermalization of the excited Auger electrons and photoelectrons. We explain the dependence of the photoacoustic signal S on photon energy and the proportionality to the x-ray absorption coefficient in agreement with recent experiments on Cu. Results are presented for the dependence of S on photon energy, sample thickness, and the electronic structure of the absorbing solid.

Theory for the optical properties of small Hg_n clusters

The static and dynamical polarizabilities of the Hg-dimer are calculated by using a Hubbard Hamiltonian to describe the electronic structure. The Hamiltonian is diagonalized exactly within a subspace of second-quantized electronic states from which only multiply ionized atomic configurations have been excluded. With this approximation we can describe the most important electronic transitions including the effect of charge fluctuations. We analyze the polarizability as a function of the intraatomic Coulomb interaction which represents the repulsion between electrons. We obtain that this interaction results in strong electronic correlations in the excited states and increases the first excitation energy of the dimer by 0.8 eV in comparison to a calculation which neglects correlations, resulting in a better agreement with the experiment.

{2p_\pi}-{2p_\sigma} crossing in heavy symmetric ion-atom collisions: I. Level structure

Ab initio self-consistent DFS calculations are performed for five different symmetric atomic systems from Ar-Ar to Pb-Pb. The level structure for the {2p_\pi}-{2p_\sigma} crossing as function of the united atomic charge Z_u is studied and interpreted. Manybody effects, spin-orbit splitting, direct relativistic effects as well as indirect relativistic effects are differently important for different Z_u. For the I-I system a comparison with other calculations is given.

Quadrupole moments of radium isotopes from the 7p^2P_3/2 hyperfine structure in Ra II

The hyperfine structure and isotope shift of ^{221- 226}Ra and ^{212, 214}Ra have been measured in the ionic (Ra 11) transition 7s^2 S_{1/2} - 7p ^2 P_{3/2} (\lamda = 381.4 nm). The method of on-line collinear fast-beam laser spectroscopy has been applied using frequency-doubling of cw dye laser radiation in an external ring cavity. The magnetic hyperfine fields are compared with semi-empirical and ab initio calculations. The analysis of the quadrupole splitting by the same method yields the following, improved values of spectroscopic quadrupole moments: Q_s(^221 Ra)= 1.978(7)b, Q_s (^223 Ra)= 1.254(3)b and the reanalyzed values Q_s(^209 Ra) = 0.40(2)b, Q_s(^211 Ra) = 0.48(2)b, Q_s(^227 Ra)= 1.58(3)b, Q_s (^229 Ra) = 3.09(4)b with an additional scaling uncertainty of ±5%. Furthermore, the J-dependence of the isotope shift is analyzed in both Ra II transitions connecting the 7s^2 S_{1/2} ground state with the first excited doublet 7p^ P_{1/2} and 7p^ P_{3/2}.

Non-relativistic and relativistic molecular calculations for the chalcogen hexafluorides: SF_6, SeF_6, TeF_6, PoF_6

Non-relativistic Hartree-Fock-Slater and relativistic Dirac-Slater self-consistent orbital models are applied for the analysis of the electronic structure of the chalcogen hexafluorides: SF_6, SeF_6, TeF_6 and PoF_6. The molecular eigenfunctions and eigenvalues are generated using the discrete variational method (DVM) with numerical basis functions. The results obtained for SF_6 are compared with other ab initio calculations. Information about relativistic level shifts and spin-orbit splitting has been obtained by comparison between the non-relativistic and relativistic results.

Exploring chromium (VI) dioxodihalides chemistry: is density functional theory the most suitable tool?

A comparative systematic study of the CrO2F2 compound has been performed using different conventional ab initio methodologies and density functional procedures. Two points have been analyzed: first, the accuracy of results yielded by each method under study, and second, the computational cost required to reach such results. Weighing up both aspects, density functional theory has been found to be more appropriate than the Hartree-Fock (HF) and the analyzed post-HF methods. Hence, the structural characterization and spectroscopic elucidation of the full CrO2X2 series (X=F,Cl,Br,I) has been done at this level of theory. Emphasis has been given to the unknown CrO2I2 species, and specially to the UV/visible spectra of all four compounds. Furthermore, a topological analysis in terms of charge density distributions has revealed why the valence shell electron pair repulsion model fails in predicting the molecular shape of such CrO2X2 complexes

The equilibrium structure of monofluoroacetylene

The equilibrium rotational constants Be of HCCF and DCCF have been determined from the ground state rotational constants B0, by determining the αr constants for all five fundamentals from the high-resolution vibrational—rotation spectrum making appropriate corrections for the effects of Fermi resonance. By combination with results from the 13C isotopomers and the recent ab initio calculations by Botschwina (Chem. Phys. Lett., 209 (1993) 117), the equilibrium structure is deduced to be: re(CH) = 1.0555(15) Å, re(CC) = 1.1955(8) Å and re(CF) = 1.2781(8) Å.

The molecular structure of hexamethyldigermane determined by gas-phase electron diffraction with theoretical calculations for (CH3)3M-M(CH3)3 Where M = C, Si, and Ge

Gas-phase electron diffraction (GED) data together with results from ab initio molecular orbital calculations (HF and MP2/6-311+G(d,p)) have been used to determine the structure of hexamethyldigermane ((CH3)3Ge-Ge(CH3)3). The equilibrium symmetry is D3d, but the molecule has a very low-frequency, largeamplitude, torsional mode (φCGeGeC) that lowers the thermal average symmetry. The effect of this largeamplitude mode on the interatomic distances was described by a dynamic model which consisted of a set of pseudoconformers spaced at even intervals. The amount of each pseudoconformer was obtained from the ab initio calculations (HF/6-311+G(d,p)). The results for the principal distances (ra) and angles (∠h1) obtained from the combined GED/ab initio (with estimated 1σ uncertainties) are r(Ge-Ge) ) 2.417(2) Å, r(Ge-C) ) 1.956(1) Å, r(C-H) ) 1.097(5) Å, ∠GeGeC ) 110.5(2)°, and ∠GeCH ) 108.8(6)°. Theoretical calculations were performed for the related molecules ((CH3)3Si-Si(CH3)3 and (CH3)3C-C(CH3)3).

The vibrational spectrum and ultimate modulus of polyethylene

We have performed the first completely ab initio lattice dynamics calculation of the full orthorhombic cell of polyethylene using periodic density functional theory in the local density approximation (LDA) and the generalized gradient approximation (GGA). Contrary to current perceptions, we show that LDA accurately describes the structure whereas GGA fails. We emphasize that there is no parametrization of the results. We then rigorously tested our calculation by computing the phonon dispersion curves across the entire Brillouin zone and comparing them to the vibrational spectra, in particular the inelastic neutron scattering (INS) spectra, of polyethylene (both polycrystalline and aligned) and perdeuteriopolyethylene. The F-point frequencies (where the infrared and Raman active modes occur) are in good agreement with the latest low temperature data. The near-perfect reproduction of the INS spectra, gives confidence in the results and allows Lis to deduce a number of physical properties including the elastic moduli, parallel and perpendicular to the chain. We find that the Young's modulus for an infinitely long, perfectly crystalline polyethylene is 360.2 GPa at 0 K. The highest experimental value is 324 GPa, indicating that current high modulus fibers are similar to 90% of their maximum possible strength.

A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

A case of four-coordinate silver(I) adopting a high energy planar geometry. Experiment and theory

The ligands PhL and MeL are obtained by condensing 2-formylpyridine with benzil dihydrazone and diacetyl dihydrazone, respectively, in 2: 1 molar proportion. With silver( I), PhL yields a double-stranded dinuclear cationic helicate 1 in which the metal is tetrahedral but MeL gives a cationic one-dimensional polymeric complex 2 where silver( I) is distorted square planar and the ligand backbone is nearly planar. In both complexes, metal: ligand ratio is 1: 1. Ab initio calculations on the ligands at the HF/6-31+G* level reveal that while PhL strongly prefers a helical conformation, MeL has a natural inclination to remain in a planar conformation. Density functional theory calculations on model silver( I) complexes show that formation of the linear polymer in the case of MeL is also an important factor in imposing the planar geometry of Ag(I) in 2.