Stone-Wales Transformation Paths in Fullerene C60

The mechanisms of formation of a metastable defect isomer of fullerene C60 due to the Stone-Wales transformation are theoretically studied. It is demonstrated that the paths of the "dynamic" Stone-Wales transformation at a high sufficient for overcoming potential barriers) temperature can differ from the two "adiabatic" transformation paths discussed in the literature. This behavior is due to the presence of a great near-flat segment of the potential-energy surface in the neighborhood of metastable states. Besides, the sequence of rupture and formation of interatomic bonds is other than that in the case of the adiabatictransformation.Comment: 10 pages, 6 figure

Vibrational signatures for low-energy intermediate-sized Si clusters

We report low-energy locally stable structures for the clusters Si20 and Si21. The structures were obtained by performing geometry optimizations within the local density approximation. Our calculated binding energies for these clusters are larger than any previously reported for this size regime. To aid in the experimental identification of the structures, we have computed the full vibrational spectra of the clusters, along with the Raman and IR activities of the various modes using a recently developed first-principles technique. These represent, to our knowledge, the first calculations of Raman and IR spectra for Si clusters of this size

Observation and Assignment of Silent and Higher Order Vibrations in the Infrared Transmission of C60 Crystals

We report the measurement of infrared transmission of large C60 single crystals. The spectra exhibit a very rich structure with over 180 vibrational absorptions visible in the 100 - 4000 cm-1 range. Many silent modes are observed to have become weakly IR-active. We also observe a large number of higher order combination modes. The temperature (77K - 300K) and pressure (0 - 25KBar) dependencies of these modes were measured and are presented. Careful analysis of the IR spectra in conjunction with Raman scattering data showing second order modes and neutron scattering data, allow the selection of the 46 vibrational modes C60. We are able to fit *all* of the first and second order data seen in the present IR spectra and the previously published Raman data (~300 lines total), using these 46 modes and their group theory allowed second order combinations.Comment: REVTEX v3.0 in LaTeX. 12 pages. 8 Figures by request. c60lon

Exchange-correlation kernels for excited states in solids

The performance of several common approximations for the exchange-correlation kernel within time-dependent density-functional theory is tested for elementary excitations in the homogeneous electron gas. Although the adiabatic local-density approximation gives a reasonably good account of the plasmon dispersion, systematic errors are pointed out and traced to the neglect of the wavevector dependence. Kernels optimized for atoms are found to perform poorly in extended systems due to an incorrect behavior in the long-wavelength limit, leading to quantitative deviations that significantly exceed the experimental error bars for the plasmon dispersion in the alkali metals.Comment: 7 pages including 5 figures, RevTe

The Effect of Lattice Vibrations on Substitutional Alloy Thermodynamics

A longstanding limitation of first-principles calculations of substitutional alloy phase diagrams is the difficulty to account for lattice vibrations. A survey of the theoretical and experimental literature seeking to quantify the impact of lattice vibrations on phase stability indicates that this effect can be substantial. Typical vibrational entropy differences between phases are of the order of 0.1 to 0.2 k_B/atom, which is comparable to the typical values of configurational entropy differences in binary alloys (at most 0.693 k_B/atom). This paper describes the basic formalism underlying ab initio phase diagram calculations, along with the generalization required to account for lattice vibrations. We overview the various techniques allowing the theoretical calculation and the experimental determination of phonon dispersion curves and related thermodynamic quantities, such as vibrational entropy or free energy. A clear picture of the origin of vibrational entropy differences between phases in an alloy system is presented that goes beyond the traditional bond counting and volume change arguments. Vibrational entropy change can be attributed to the changes in chemical bond stiffness associated with the changes in bond length that take place during a phase transformation. This so-called ``bond stiffness vs. bond length'' interpretation both summarizes the key phenomenon driving vibrational entropy changes and provides a practical tool to model them.Comment: Submitted to Reviews of Modern Physics 44 pages, 6 figure

Superconductivity in Fullerides

Experimental studies of superconductivity properties of fullerides are briefly reviewed. Theoretical calculations of the electron-phonon coupling, in particular for the intramolecular phonons, are discussed extensively. The calculations are compared with coupling constants deduced from a number of different experimental techniques. It is discussed why the A_3 C_60 are not Mott-Hubbard insulators, in spite of the large Coulomb interaction. Estimates of the Coulomb pseudopotential $\mu^*$, describing the effect of the Coulomb repulsion on the superconductivity, as well as possible electronic mechanisms for the superconductivity are reviewed. The calculation of various properties within the Migdal-Eliashberg theory and attempts to go beyond this theory are described.Comment: 33 pages, latex2e, revtex using rmp style, 15 figures, submitted to Review of Modern Physics, more information at http://radix2.mpi-stuttgart.mpg.de/fullerene/fullerene.htm

Phonons and related properties of extended systems from density-functional perturbation theory

This article reviews the current status of lattice-dynamical calculations in crystals, using density-functional perturbation theory, with emphasis on the plane-wave pseudo-potential method. Several specialized topics are treated, including the implementation for metals, the calculation of the response to macroscopic electric fields and their relevance to long wave-length vibrations in polar materials, the response to strain deformations, and higher-order responses. The success of this methodology is demonstrated with a number of applications existing in the literature.Comment: 52 pages, 14 figures, submitted to Review of Modern Physic

Fully Metal-Coated Scanning Near-Field Optical Microscopy Probes with Spiral Corrugations for Superfocusing under Arbitrarily Oriented Linearly Polarised Excitation

We study the effect of a spiral corrugation on the outer surface of a fully metal-coated scanning near-field optical microscopy (SNOM) probe using the finite element method. The introduction of a novel form of asymmetry, devoid of any preferential spatial direction and covering the whole angular range of the originally axisymmetric tip, allows attaining strong field localization for a linearly polarised mode with arbitrary orientation. Compared to previously proposed asymmetric structures which require linearly polarised excitation properly oriented with respect to the asymmetry, such a configuration enables significant simplification in mode injection. In fact, not only is the need for the delicate procedure to generate radially polarised beams overcome, but also the relative alignment between the linearly polarised beam and the tip modification is no longer critical

Functional Diversity of Human Basic Helix-Loop-Helix Transcription Factor TCF4 Isoforms Generated by Alternative 5′ Exon Usage and Splicing

BACKGROUND: Transcription factor 4 (TCF4 alias ITF2, E2-2, ME2 or SEF2) is a ubiquitous class A basic helix-loop-helix protein that binds to E-box DNA sequences (CANNTG). While involved in the development and functioning of many different cell types, recent studies point to important roles for TCF4 in the nervous system. Specifically, human TCF4 gene is implicated in susceptibility to schizophrenia and TCF4 haploinsufficiency is the cause of the Pitt-Hopkins mental retardation syndrome. However, the structure, expression and coding potential of the human TCF4 gene have not been described in detail. PRINCIPAL FINDINGS: In the present study we used human tissue samples to characterize human TCF4 gene structure and TCF4 expression at mRNA and protein level. We report that although widely expressed, human TCF4 mRNA expression is particularly high in the brain. We demonstrate that usage of numerous 5' exons of the human TCF4 gene potentially yields in TCF4 protein isoforms with 18 different N-termini. In addition, the diversity of isoforms is increased by alternative splicing of several internal exons. For functional characterization of TCF4 isoforms, we overexpressed individual isoforms in cultured human cells. Our analysis revealed that subcellular distribution of TCF4 isoforms is differentially regulated: Some isoforms contain a bipartite nuclear localization signal and are exclusively nuclear, whereas distribution of other isoforms relies on heterodimerization partners. Furthermore, the ability of different TCF4 isoforms to regulate E-box controlled reporter gene transcription is varied depending on whether one or both of the two TCF4 transcription activation domains are present in the protein. Both TCF4 activation domains are able to activate transcription independently, but act synergistically in combination. CONCLUSIONS: Altogether, in this study we have described the inter-tissue variability of TCF4 expression in human and provided evidence about the functional diversity of the alternative TCF4 protein isoforms