Gold as intermolecular glue: a theoretical study of nanostrips based on quinoline-type monomers

A family of infinite nanostrips is computationally predicted. In it monomers of single, double or triple aromatic rings are linked to each other by strong C-Au-C, C-Au <-- N or N --> Au <-- N bonds. Depending on the geometry of the system and saturation of the bonds, these 1-D nanostrips are found to be insulators, narrow- or zero-gap semiconductors, or metals. The calculated dimerization and polymerization energies suggest clear exothermicity of formation. Varying the nitrogen content in the aromatic ring is found to little affect the geometry, and the 1-D band structure of the strips can be interpreted in a rigid-band picture. The orbital character of the states at the Fermi level has been analyzed. One of the new structures is found to be closely similar to graphene with respect to its band structure properties.     

Theoretical chemistry of gold

Gold is an element whose unique properties are strongly influenced by relativistic effects. A large body of appropriate calculations now exist and their main conclusions are summarized. The theoretical interpretation of the aurophilic attraction is discussed in detail.     

Structure and stability of gold-substituted diborane, boranes, and borohydride ions

Pseudopotential ab initio calculations were performed for species of the type BH _n (AuPH₃) _m ^k , where n+m=3 or 4, and the charge k is −2,…,+1. Some derivatives of these and diaurated diboranes were also studied. The structural data agree well with the available experimental evidence. Factors affecting the stability of these systems, including the role of aurophilic attraction, are discussed. The singly charged anions and the diaurated diboranes are predicted to be the most stable members of these series. Received: 22 January 1999 / Accepted: 2 June 1999 / Published online: 4 October 1999     

Gold as intermolecular glue: a predicted planar triaurotriazine, C3Au3N3, isomer of gold cyanide

It is predicted that solid gold cyanide, AuCN, could have an alternative infinite trigonal-sheet crystal structure, of almost the same energy as the known hexagonally-packed infinite-chain structure.     

A suggested periodic table up to Z≤ 172, based on Dirac-Fock calculations on atoms and ions

Extended Average Level (EAL) Dirac-Fock calculations on atoms and ions agree with earlier work in that a rough shell-filling order for the elements 119-172 is 8s < 5g≤ 8p(1/2) < 6f < 7d < 9s < 9p(1/2) < 8p(3/2). The present Periodic Table develops further that of Fricke, Greiner and Waber [Theor. Chim. Acta 1971, 21, 235] by formally assigning the elements 121-164 to (nlj) slots on the basis of the electron configurations of their ions. Simple estimates are made for likely maximum oxidation states, i, of these elements M in their MX(i) compounds, such as i = 6 for UF(6). Particularly high i are predicted for the 6f elements.     

Understanding the Uniqueness of 2p Elements in Periodic Tables

The Periodic Table, and the unique chemical behavior of the first element in a column (group), were discovered simultaneously one and a half centuries ago. Half a century ago, this unique chemistry of the light homologs was correlated to the then available atomic orbital (AO) radii. The radially nodeless 1s, 2p, 3d, 4f valence AOs are particularly compact. The similarity of r (2s)≈r(2p) leads to pronounced sp-hybrid bonding of the light p-block elements, whereas the heavier p elements with n≥3 exhibit r (ns) ≪ r (np) of approximately −20 to −30 % . Herein, a comprehensive physical explanation is presented in terms of kinetic radial and angular, as well as potential nuclear-attraction and electron-screening effects. For hydrogen-like atoms and all inner shells of the heavy atoms, r (2s) ≫ r (2p) by +20 to +30 % , whereas r (3s)≳r(3p) ≳r(3d), since in Coulomb potentials radial motion is more radial orbital expanding than angular motion. However, the screening of nuclear attraction by inner core shells is more efficient for s than for p valence shells. The uniqueness of the 2p AO is explained by this differential shielding. Thereby, the present work paves the way for future physical explanations of the 3d, 4f, and 5g cases.     

Method for detecting small changes in vibrotactile perception threshold related to tactile acuity

Two metrics, expressing the change in mechanoreceptor-specific vibrotactile thresholds at a fingertip over a time interval of months or years, and the shift in threshold from the mean values recorded from the fingertips of healthy persons, have been constructed for thresholds measured from individual fingers. The metrics assume the applicability of the acute adaptation property of mechanoreceptors, which has been confirmed by thresholds obtained from 18 forest workers on two occasions, separated by 5 years. Hence, when expressed in decibels, both threshold changes and threshold shifts may be averaged at frequencies mediated by the same receptor population to improve precision. Differences between threshold changes at frequencies mediated by the same receptor population may be used to identify inconsistent subject performance, and hence potentially erroneous results. For this group of subjects, the threshold changes and threshold shifts at frequencies believed mediated by the slowly adapting type I (SAI) (4 and 6.3 Hz) and rapidly adapting type I (FAI) (20 and 32 Hz) receptors within each finger were correlated. In these circumstances, which may be expected to occur for some work-induced and systemic peripheral neuropathies, both threshold changes and threshold shifts may be summed over SAI and FAI receptors to improve precision, and hence the potential for interpretation.     

A London-type formula for the dispersion interactions of endohedral A@B systems

A London-type formula is derived for endohedral systems. It involves the static dipole polarisability, alpha(1)(A) of the inner system, A, and a new type of dipole polarisability, alpha(-2)(B) with an r(-2) radial operator, for the outer system, B. The new formula has no explicit dependence on the radius, R, of B. The predicted interaction energies are compared against MP2 supermolecular calculations for A@C(60), A = He-Xe, Zn, Cd, Hg, and CH(4).