1,477 research outputs found
Crystal Structures of Polymerized Fullerides AC60, A=K, Rb, Cs and Alkali-mediated Interactions
Starting from a model of rigid interacting C60 polymer chains on an
orthorhombic lattice, we study the mutual orientation of the chains and the
stability of the crystalline structures Pmnn and I2/m. We take into account i)
van der Waals interactions and electric quadrupole interactions between C60
monomers on different chains as well as ii) interactions of the monomers with
the surrounding alkali atoms. The direct interactions i) always lead to an
antiferrorotational structure Pmnn with alternate orientation of the C60 chains
in planes (001). The interactions ii) with the alkalis consist of two parts:
translation-rotation (TR) coupling where the orientations of the chains
interact with displacements of the alkalis, and quadrupolar electronic
polarizability (ep) coupling, where the electric quadrupoles on the C60
monomers interact with induced quadrupoles due to excited electronic d states
of the alkalis. Both interactions ii) lead to an effective
orientation-orientation interaction between the C60 chains and always favor the
ferrorotational structure I2/m where C60 chains have a same orientation. The
structures Pmnn for KC60 and I2/m for Rb- and CsC60 are the result of a
competition between the direct interaction i) and the alkali-mediated
interactions ii). In Rb- and CsC60 the latter are found to be dominant, the
preponderant role being played by the quadrupolar electronic polarizability of
the alkali ions.Comment: J.Chem.Phys., in press, 14 pages, 3 figures, 8 table
Analytical Two-valued Potential Energy Functions for the Ground State Surfaces of CO2 and CS2
A potential model for two-valued triatomic surfaces is
reviewed with reference to the ground state potentials O·f
02(X11;g+) and CS2(X11:g+) . A comparison is made between the
observed J = O vibrational spectra and those calculated from
the derived potentia1ls by a variational method. For C02 the
strong Fermi-resonance in the (10"0) and (02°0) vibrational states
is confirmed for the first time using a full three-dimensional
potential and a complete vibrational hamiltonian
Antiferromagnetic Exchange Interaction between Electrons on Degenerate LUMOs in Benzene Dianion
We discuss the ground state of Benzene dianion (Bz) on the basis of
the numerical diagonalization method of an effective model of orbitals.
It is found that the ground state can be the spin singlet state, and the
exchange coupling between LUMOs can be antiferromagnetic.Comment: Accepted for publication in J. Phys. Soc. Jpn., 2 pages, 3 figure
Extended Huckel theory for bandstructure, chemistry, and transport. II. Silicon
In this second paper, we develop transferable semi-empirical parameters for
the technologically important material, silicon, using Extended Huckel Theory
(EHT) to calculate its electronic structure. The EHT-parameters areoptimized to
experimental target values of the band dispersion of bulk-silicon. We obtain a
very good quantitative match to the bandstructure characteristics such as
bandedges and effective masses, which are competitive with the values obtained
within an orthogonal-tight binding model for silicon. The
transferability of the parameters is investigated applying them to different
physical and chemical environments by calculating the bandstructure of two
reconstructed surfaces with different orientations: Si(100) (2x1) and Si(111)
(2x1). The reproduced - and -surface bands agree in part
quantitatively with DFT-GW calculations and PES/IPES experiments demonstrating
their robustness to environmental changes. We further apply the silicon
parameters to describe the 1D band dispersion of a unrelaxed rectangular
silicon nanowire (SiNW) and demonstrate the EHT-approach of surface passivation
using hydrogen. Our EHT-parameters thus provide a quantitative model of
bulk-silicon and silicon-based materials such as contacts and surfaces, which
are essential ingredients towards a quantitative quantum transport simulation
through silicon-based heterostructures.Comment: 9 pages, 9 figure
A tight binding model for water
We demonstrate for the first time a tight binding model for water
incorporating polarizable anions. A novel aspect is that we adopt a "ground up"
approach in that properties of the monomer and dimer only are fitted.
Subsequently we make predictions of the structure and properties of hexamer
clusters, ice-XI and liquid water. A particular feature, missing in current
tight binding and semiempirical hamiltonians, is that we reproduce the almost
two-fold increase in molecular dipole moment as clusters are built up towards
the limit of bulk liquid. We concentrate on properties of liquid water which
are very well rendered in comparison with experiment and published density
functional calculations. Finally we comment on the question of the contrasting
densities of water and ice which is central to an understanding of the
subtleties of the hydrogen bond
State-to-State Differential and Relative Integral Cross Sections for Rotationally Inelastic Scattering of H2O by Hydrogen
State-to-state differential cross sections (DCSs) for rotationally inelastic
scattering of H2O by H2 have been measured at 71.2 meV (574 cm-1) and 44.8 meV
(361 cm-1) collision energy using crossed molecular beams combined with
velocity map imaging. A molecular beam containing variable compositions of the
(J = 0, 1, 2) rotational states of hydrogen collides with a molecular beam of
argon seeded with water vapor that is cooled by supersonic expansion to its
lowest para or ortho rotational levels (JKaKc= 000 and 101, respectively).
Angular speed distributions of fully specified rotationally excited final
states are obtained using velocity map imaging. Relative integral cross
sections are obtained by integrating the DCSs taken with the same experimental
conditions. Experimental state-specific DCSs are compared with predictions from
fully quantum scattering calculations on the most complete H2O-H2 potential
energy surface. Comparison of relative total cross sections and state-specific
DCSs show excellent agreement with theory in almost all detailsComment: 46 page
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the -network
Semiconductor glasses exhibit many unique optical and electronic anomalies.
We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508
(2010)) in which several of these anomalies arise from deep midgap electronic
states residing on high-strain regions intrinsic to the activated transport
above the glass transition. Here we demonstrate at the molecular level how this
scenario is realized in an important class of semiconductor glasses, namely
chalcogen and pnictogen containing alloys. Both the glass itself and the
intrinsic electronic midgap states emerge as a result of the formation of a
network composed of -bonded atomic -orbitals that are only weakly
hybridized. Despite a large number of weak bonds, these -networks are
stable with respect to competing types of bonding, while exhibiting a high
degree of structural degeneracy. The stability is rationalized with the help of
a hereby proposed structural model, by which -networks are
symmetry-broken and distorted versions of a high symmetry structure. The latter
structure exhibits exact octahedral coordination and is fully
covalently-bonded. The present approach provides a microscopic route to a fully
consistent description of the electronic and structural excitations in vitreous
semiconductors.Comment: 22 pages, 17 figures, revised version, final version to appear in J.
Chem. Phy
Draft genome sequence of Methyloferula stellata AR4, an obligate methanotroph possessing only a soluble methane monooxygenase
Methyloferula stellata AR4 is an aerobic acidophilic methanotroph, which, in contrast to most known methanotrophs but similar to Methylocella spp., possesses only a soluble methane monooxygenase. However, it differs from Methylocella spp. by its inability to grow on multicarbon substrates. Here, we report the draft genome sequence of this bacterium
The Melting Points of the Inert Gas Solids
The melting points of the heavy inert gases and of some other simple molecules show an excellent
linear correlation with the depths of their diatomic potential wells, and the slope of the
correlation line is in accord with Lindemann’s theory of melting
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