Atomic spectral-product representations of molecular electronic structure: metric matrices and atomic-product composition of molecular eigenfunctions

Recent progress is reported in development of ab initio computational methods for the electronic structures of molecules employing the many-electron eigenstates of constituent atoms in spectral-product forms. The approach provides a universal atomic-product description of the electronic structure of matter as an alternative to more commonly employed valence-bond- or molecular-orbital-based representations. The Hamiltonian matrix in this representation is seen to comprise a sum over atomic energies and a pairwise sum over Coulombic interaction terms that depend only on the separations of the individual atomic pairs. Overall electron antisymmetry can be enforced by unitary transformation when appropriate, rather than as a possibly encumbering or unnecessary global constraint. The matrix representative of the antisymmetrizer in the spectral-product basis, which is equivalent to the metric matrix of the corresponding explicitly antisymmetric basis, provides the required transformation to antisymmetric or linearly independent states after Hamiltonian evaluation. Particular attention is focused in the present report on properties of the metric matrix and on the atomic-product compositions of molecular eigenstates as described in the spectral-product representations. Illustrative calculations are reported for simple but prototypically important diatomic (H_2, CH) and triatomic (H_3, CH_2) molecules employing algorithms and computer codes devised recently for this purpose. This particular implementation of the approach combines Slater-orbital-based one- and two-electron integral evaluations, valence-bond constructions of standard tableau functions and matrices, and transformations to atomic eigenstate-product representations. The calculated metric matrices and corresponding potential energy surfaces obtained in this way elucidate a number of aspects of the spectral-product development, including the nature of closure in the representation, the general redundancy or linear dependence of its explicitly antisymmetrized form, the convergence of the apparently disparate atomic-product and explicitly antisymmetrized atomic-product forms to a common invariant subspace, and the nature of a chemical bonding descriptor provided by the atomic-product compositions of molecular eigenstates. Concluding remarks indicate additional studies in progress and the prognosis for performing atomic spectral-product calculations more generally and efficiently

Spin transport in inhomogeneous magnetic fields: a proposal for Stern-Gerlach-like experiments with conduction electrons

Spin dynamics in spatially inhomogeneous magnetic fields is studied within the framework of Boltzmann theory. Stern-Gerlach-like separation of spin up and spin down electrons occurs in ballistic and diffusive regimes, before spin relaxation sets in. Transient dynamics and spectral response to time-dependent inhomogeneous magnetic fields are investigated, and possible experimental observations of our findings are discussed.Comment: 7 pages, 4 figures; revised and extended version, to appear in PR

Why Global Inequality Matters: Derivative Global Egalitarianism

This article integrates empirical and normative discussions about why global economic inequalities matter in critically examining an approach known as derivative global egalitarianism (DGE). DGE is a burgeoning perspective that opposes excessive global economic inequality not based on the intrinsic value of equality but inequality\u27s negative repercussions on other values. The article aims to advance the research agenda by identifying and critically evaluating four primary varieties of DGE arguments from related but distinct literatures, which span a number of disciplines, including economics, international relations, and political philosophy. Overall, DGE offers a number of persuasive arguments as to why current levels of global inequality are of concern, but aspects of DGE beg further philosophical and empirical examination. By situating DGE within the wider theoretical and empirical contexts, this article provides resources for its critical assessment and theoretical development

Delayed self-recognition in children with autism spectrum disorder.

This study aimed to investigate temporally extended self-awareness (awareness of one’s place in and continued existence through time) in autism spectrum disorder (ASD), using the delayed self-recognition (DSR) paradigm (Povinelli et al., Child Development 67:1540–1554, 1996). Relative to age and verbal ability matched comparison children, children with ASD showed unattenuated performance on the DSR task, despite showing significant impairments in theory-of-mind task performance, and a reduced propensity to use personal pronouns to refer to themselves. The results may indicate intact temporally extended self-awareness in ASD. However, it may be that the DSR task is not an unambiguous measure of temporally extended self-awareness and it can be passed through strategies which do not require the possession of a temporally extended self-concept