The Influence of Halide Substituents on the Structural and Magnetic Properties of Fe6_{6}Dy3_{3} Rings

We report the synthesis and magnetic properties of three new nine-membered Fe(III)-Dy(III) cyclic coordination clusters (CCCs), with a core motif of [Fe$_{6}$Dy$_{3}$(μ-OMe)$_{9}$(vanox)$_{6}$(X-benz)$_{6}$] where the benzoate ligands are substituted in the para-position with X = F (1), Cl (2), Br (3). Single crystal X-ray diffraction structure analyses show that for the smaller fluorine or chlorine substituents the resulting structures exhibit an isostructural Fe$_{6}$Dy$_{3}$ core, whilst the 4-bromobenzoate ligand leads to structural distortions which affect the dynamic magnetic behavior. The magnetic susceptibility and magnetization of 1-3 were investigated and show similar behavior in the dc (direct current) magnetic data. Additional ac (alternating current) magnetic measurements show that all compounds exhibit frequency-dependent and temperature-dependent signals in the in-phase and out-of-phase component of the susceptibility and can therefore be described as field-induced SMMs. The fluoro-substituted benzoate cluster 1 shows a magnetic behavior closely similar to that of the corresponding unsubstituted Fe$_{6}$Dy$_{3}$ cluster, with U$_{eff}$ = 21.3 K within the Orbach process. By increasing the size of the substituent toward 4-chlorobenzoate within 2, an increase of the energy barrier to U$_{eff}$ = 36.1 K was observed. While the energy barrier becomes higher from 1 to 2, highlighting that the introduction of different substituents on the benzoate ligand in the para-position has an impact on the magnetic properties, cluster 3 shows a significantly different SMM behavior where U$_{eff}$ is reduced in the Orbach regime to only 4.9 K

Electronic excitations and electron-phonon coupling in bulk graphite through Raman scattering in high magnetic fields

We use polarized magneto-Raman scattering to study purely electronic excitations and the electron-phonon coupling in bulk graphite. At a temperature of 4.2 K and in magnetic fields up to 28 T we observe $K$-point electronic excitations involving Landau bands with $\Delta |n|=0$ and with $\Delta |n|=\pm2$ that can be selected by controlling the angular momentum of the excitation laser and of the scattered light. The magneto-phonon effect involving the $E_{2g}$ optical phonon and $K$-point inter Landau bands electronic excitations with $\Delta |n|=\pm1$ is revealed and analyzed within a model taking into account the full $k_z$ dispersion. These polarization resolved results are explained in the frame of the Slonczewski-Weiss-McClure (SWM) model which directly allows to quantify the electron-hole asymmetry.Comment: 13 pages, 10 figure

Modeling and Simulation of Multi-Lane Traffic Flow

A most important aspect in the field of traffic modeling is the simulation of bottleneck situations. For their realistic description a macroscopic multi-lane model for uni-directional freeways including acceleration, deceleration, velocity fluctuations, overtaking and lane-changing maneuvers is systematically deduced from a gas-kinetic (Boltzmann-like) approach. The resulting equations contain corrections with respect to previous models. For efficient computer simulations, a reduced model delineating the coarse-grained temporal behavior is derived and applied to bottleneck situations.Comment: For related work see http://www.theo2.physik.uni-stuttgart.de/helbing.htm

Photocatalytic water splitting reaction catalyzed by ion-exchanged salts of potassium poly(heptazine imide) 2D materials

Potassium poly (heptazine imide) (K-PHI), a crystalline two-dimensional carbon–nitride material, is an active photocatalyst for water splitting. The potassium ions in K-PHI can be exchanged with other ions to change the properties of the material and eventually to design the catalysts. We report here the electronic structures of several ion-exchanged salts of K-PHI (K, H, Au, Ru, and Mg) and their feasibility as water splitting photocatalysts, which were determined by density functional theory (DFT) calculations. The DFT results are complemented by experiments where the performances in the photocatalytic hydrogen evolution reaction (HER) were recorded. We show that due to its narrow band gap, Ru-PHI is not a suitable photocatalyst. The water oxidation potentials are straddled between the band edge potentials of H-PHI, Au-PHI, and Mg-PHI; thus, these are active photocatalysts for both the oxygen and hydrogen evolution reactions, whereas K-PHI is active only for the HER. The experimental data show that these are active HER photocatalysts, in agreement with the DFT results. Furthermore, Mg-PHI has shown remarkable performance in the HER, with a rate of 539 μmol/(h·g) and a quantum efficiency of 7.14% at 410 nm light irradiation, which could be due to activation of the water molecule upon adsorption, as predicted by our DFT calculations

The First Use of a ReX5_{5} Synthon to Modulate FeIII^{III} Spin Crossover via Supramolecular Halogen⋅⋅⋅Halogen Interactions

We have added the {Re$^{IV}$X$_{5}$}$^{−}$ (X=Br, Cl) synthon to a pocket‐based ligand to provide supramolecular design using halogen⋅⋅⋅halogen interactions within an Fe$^{III}$ system that has the potential to undergo spin crossover (SCO). By removing the solvent from the crystal lattice, we “switch on” halogen⋅⋅⋅halogen interactions between neighboring molecules, providing a supramolecular cooperative pathway for SCO. Furthermore, changes to the halogen‐based interaction allow us to modify the temperature and nature of the SCO event

Magneto-Raman scattering of graphene on graphite: Electronic and phonon excitations

Magneto-Raman scattering experiments from the surface of graphite reveal novel features associated to purely electronic excitations which are observed in addition to phonon-mediated resonances. Graphene-like and graphite domains are identified through experiments with $\sim 1\mu m$ spatial resolution performed in magnetic fields up to 32T. Polarization resolved measurements emphasize the characteristic selection rules for electronic transitions in graphene. Graphene on graphite displays the unexpected hybridization between optical phonon and symmetric across the Dirac point inter Landau level transitions. The results open new experimental possibilities - to use light scattering methods in studies of graphene under quantum Hall effect conditions.Comment: 4 pages, 5 figures; revised manuscript with additional dat

Critical exponents and intrinsic broadening of the field-induced transition in NiCl2_2⋅\cdot4SC(NH2_2)2_2

The field-induced ordering transition in the quantum spin system NiCl$_2$$\cdot$4SC(NH$_2$)$_2$ is studied by means of neutron diffraction, AC magnetometry and relaxation calorimetry. The interpretation of the data is strongly influenced by a finite distribution of transition fields in the samples, which was present but disregarded in previous studies. Taking this effect into account, we find that the order-parameter critical exponent is inconsistent with the BEC universality class even at temperatures below 100 mK. All results are discussed in comparison with previous measurements and with recent similar studies of disordered Ni(Cl$_{1-x}$Br$_x$)$_2$$\cdot$4SC(NH$_2$)$_2$

Spin-Peierls transition of the first order in S=1 antiferromagnetic Heisenberg chains

We investigate a one-dimensional S=1 antiferromagnetic Heisenberg model coupled to a lattice distortion by a quantum Monte Carlo method. Investigating the ground state energy of the static bond-alternating chain, we find that the instability to a dimerized chain depends on the value of the spin-phonon coupling, unlike the case of S=1/2. The spin state is the dimer state or the uniform Haldane state depending on whether the lattice distorts or not, respectively. At an intermediate value of the spin-phonon coupling, we find the first-order transition between the two states. We also find the coexistence of the two states.Comment: 7 pages, 12 eps figures embedded in the text; corrected typos, replaced figure

Theoretical approach to two-dimensional traffic flow models

In this paper we present a theoretical analysis of a recently proposed two-dimensional Cellular Automata model for traffic flow in cities with the novel ingredient of turning capability. Numerical simulations of this model show that there is a transition between a freely moving phase with high velocity to a jammed state with low velocity. We study the dynamics of such a model starting with the microscopic evolution equation, which will serve as a basis for further analysis. It is shown that a kinetic approach, based on the Boltzmann assumption, is able to provide a reasonably good description of the jamming transition. We further introduce a space-time continuous phenomenological model leading to a couple of partial differential equations whose preliminary results agree rather well with the numerical simulations.Comment: 15 pages, REVTeX 3.0, 7 uuencoded figures upon request to [email protected]