Homogeneous Gold Catalysis through Relativistic Effects: Addition of Water to Propyne

In the catalytic addition of water to propyne the Au(III) catalyst is not stable under non-relativistic conditions and dissociates into a Au(I) compound and Cl2. This implies that one link in the chain of events in the catalytic cycle is broken and relativity may well be seen as the reason why Au(III) compounds are effective catalysts.Comment: 12 pages, 3 figures, 1 tabl

Electronic structure and dimerization of a single monatomic gold wire

The electronic structure of a single monatomic gold wire is presented for the first time. It has been obtained with state-of-the-art ab-initio full-potential density-functional (DFT) LMTO (linearized muffin-tin orbital) calculations taking into account relativistic effects. For stretched structures in the experimentally accessible range the conduction band is exactly half-filled, whereas the band structures are more complex for the optimized structure. By studying the total energy as a function of unit-cell length and of a possible bond-length alternation we find that the system can lower its total energy by letting the bond lengths alternate leading to a structure containing separated dimers with bond lengths of about 2.5 \AA, largely independent of the stretching. However, first for fairly large unit cells (above roughly 7 \AA), is the total-energy gain upon this dimerization comparable with the energy costs upon stretching. We propose that this together with band-structure effects is the reason for the larger interatomic distances observed in recent experiments. We find also that although spin-orbit couplings lead to significant effects on the band structure, the overall conclusions are not altered, and that finite Au_2, Au_4, and Au_6 chains possess electronic properties very similar to those of the infinite chain.Comment: (14 pages, 5 figures; Elsevier Preprint style elsart.sty

Higher order Schrodinger and Hartree-Fock equations

The domain of validity of the higher-order Schrodinger equations is analyzed for harmonic-oscillator and Coulomb potentials as typical examples. Then the Cauchy theory for higher-order Hartree-Fock equations with bounded and Coulomb potentials is developed. Finally, the existence of associated ground states for the odd-order equations is proved. This renders these quantum equations relevant for physics.Comment: 19 pages, to appear in J. Math. Phy

Embedding Transition-Metal Atoms in Graphene: Structure, Bonding, and Magnetism

We present a density-functional-theory study of transition-metal atoms (Sc–Zn, Pt, and Au) embedded in single and double vacancies (SV and DV) in a graphene sheet. We show that for most metals, the bonding is strong and the metal-vacancy complexes exhibit interesting magnetic behavior. In particular, an Fe atom on a SV is not magnetic, while the Fe@DV complex has a high magnetic moment. Surprisingly, Au and Cu atoms at SV are magnetic. Both bond strengths and magnetic moments can be understood within a simple local-orbital picture, involving carbon sp2 hybrids and the metal spd orbitals. We further calculate the barriers for impurity-atom migration, and they agree well with available experimental data. We discuss the experimental realization of such systems in the context of spintronics and nanocatalysis.Peer reviewe

Common Origin for Surface Reconstruction and the Formation of Chains of Metal Atoms

During the fracture of nanocontacts gold spontaneously forms freely suspended chains of atoms, which is not observed for the iso-electronic noble metals Ag and Cu. Au also differs from Ag and Cu in forming reconstructions at its low-index surfaces. Using mechanically controllable break junctions we show that all the 5d metals that show similar reconstructions (Ir, Pt and Au) also form chains of atoms, while both properties are absent in the 4d neighbor elements (Rh, Pd, Ag), indicating a common origin for these two phenomena. A competition between s and d bonding is proposed as an explanation

g factor of Li-like ions with nonzero nuclear spin

The fully relativistic theory of the g factor of Li-like ions with nonzero nuclear spin is considered for the (1s)^2 2s state. The magnetic-dipole hyperfine-interaction correction to the atomic g factor is calculated including the one-electron contributions as well as the interelectronic-interaction effects of order 1/Z. This correction is combined with the interelectronic-interaction, QED, nuclear recoil, and nuclear size corrections to obtain high-precision theoretical values for the g factor of Li-like ions with nonzero nuclear spin. The results can be used for a precise determination of nuclear magnetic moments from g factor experiments.Comment: 20 pages, 5 figure

Origin of anomalously long interatomic distances in suspended gold chains

The discovery of long bonds in gold atom chains has represented a challenge for physical interpretation. In fact, interatomic distances frequently attain 3.0-3.6 A values and, distances as large as 5.0 A may be seldom observed. Here, we studied gold chains by transmission electron microscopy and performed theoretical calculations using cluster ab initio density functional formalism. We show that the insertion of two carbon atoms is required to account for the longest bonds, while distances above 3 A may be due to a mixture of clean and one C atom contaminated bonds.Comment: 4 pages, 4 Postscript figures, to be published in Physical Review Letter

Cross-cultural analysis of attention disengagement times supports the dissociation of faces and patterns in the infant brain

CITATION: Pyykko, J., et al. 2019. Cross-cultural analysis of attention disengagement times supports the dissociation of faces and patterns in the infant brain. Scientific Reports, 9:14414, doi:10.1038/s41598-019-51034-x.The original publication is available at https://www.nature.comInfants are slower to disengage from faces than non-face patterns when distracted by novel competing stimuli. While this perceptual predilection for faces is well documented, its universality and mechanisms in relation to other aspects of attention are poorly understood. We analysed attention disengagement times for faces and non-face patterns in a large sample of 6-to 9-month-old infants (N = 637), pooled from eye tracking studies in socioculturally diverse settings (Finland, Malawi, South Africa). Disengagement times were classified into distinct groups of quick and delayed/censored responses by unsupervised clustering. Delayed disengagement was frequent for faces (52.1% of trials), but almost negligible for patterns (3.9% of trials) in all populations. The magnitude of this attentional bias varied by individuals, whereas the impact of situational factors and facial expression was small. Individual variations in disengagement from faces were moderately stable within testing sessions and independent from variations in disengagement times for patterns. These results point to a fundamental dissociation of face and pattern processing in infants and demonstrate that the bias for faces can be robust against distractors and habituation. The results raise the possibility that attention to faces varies as an independent, early-emerging social trait in populations.https://www.nature.com/articles/s41598-019-51034-xPublisher's versio

Cohesive properties of alkali halides

We calculate cohesive properties of LiF, NaF, KF, LiCl, NaCl, and KCl with ab-initio quantum chemical methods. The coupled-cluster approach is used to correct the Hartree-Fock crystal results for correlations and to systematically improve cohesive energies, lattice constants and bulk moduli. After inclusion of correlations, we recover 95-98 % of the total cohesive energies. The lattice constants deviate from experiment by at most 1.1 %, bulk moduli by at most 8 %. We also find good agreement for spectroscopic properties of the corresponding diatomic molecules.Comment: LaTeX, 10 pages, 1 figure, accepted by Phys. Rev.

Elastic and vibrational properties of alpha and beta-PbO

The structure, electronic and dynamic properties of the two layered alpha (litharge) and beta (massicot) phases of PbO have been studied by density functional methods. The role of London dispersion interactions as leading component of the total interaction energy between layers has been addressed by using the Grimme's approach, in which new parameters for Pb and O atoms have been developed. Both gradient corrected and hybrid functionals have been adopted using Gaussian-type basis sets of polarized triple zeta quality for O atoms and small core pseudo-potential for the Pb atoms. Basis set superposition error (BSSE) has been accounted for by the Boys-Bernardi correction to compute the interlayer separation. Cross check with calculations adopting plane waves that are BSSE free have also been performed for both structures and vibrational frequencies. With the new set of proposed Grimme's type parameters structures and dynamical parameters for both PbO phases are in good agreement with experimental data.Comment: 8 pages, 5 figure