We have employed computational methods based on density functional theory to elucidate the effects of equatorial ligands on the electronic structures of trans-dioxometal complexes. In complexes with amine (sigma-only) equatorial donors, the (1)A(1 g)(b(2 g))(2)-->(1)E(g)(b(2 g))(1)(e(g))(1) excitation energy increases with metal oxidation state: Mo(IV) < Tc(V) < Ru(vi) and W(IV) < Re(V) < Os(VI). Increasing transition energies are attributed to enhanced oxometal pi-donor interactions in the higher valent central metals. But in complexes with cyanide equatorial donors, the (1)A(1 g)(b(2 g))(2)-->(1)E(g)(b(2 g))(1)(e(g))(1) energy remains roughly independent of metal oxidation state, likely owing to the compensating increased pi-donation from the pi(CN) orbitals to the metal d(xy) orbitals as the oxidation state of the metal increases.
Proton distributions at mid-rapidity (2 ≤ y ≤ 3) have been measured for 158A·GeV Pb+Pb collisions in the focusing spectrometer experiment NA44 at CERN. From baryon number conservation and by comparing the experimentally measured dNdy distribution with the transport model RQMD, we conclude that a rather high degree of nuclear stopping has been reached for the truly heavy-ion collisions at these energies. Transverse mass distributions exhibit characteristically thermal shapes and the slope parameters increase with the mass of the colliding system.
We revisit the assignment of the absorption spectrum of tetracyanonickelate(II) by calculating energies of excitations with time-dependent density functional theory. Our results give strong evidence that the original assignment of the spectrum is only partially correct. We thus propose an alternative assignment consistent with our theoretical calculations and all available experimental evidence. In particular, we reassign the bands at 22 400 and 32 300 cm(-1) to the (1)A(1g) --> (3)A(2g) (b(2g) --> b(1g)) and (1)A(1g) --> (1)A(2g) (b(2g) --> b(1g)) excitations.
Transverse mass spectra of pions, kaons, and protons from the symmetric heavy-ion collisions 200 $A$ GeV $\mathrm{S}+\mathrm{S}$ and 158 $A$ GeV $\mathrm{Pb}+\mathrm{Pb}$, measured in the NA44 focusing spectrometer at CERN, are presented. The mass dependence of the slope parameters provides evidence of collective transverse flow from expansion of the system in heavy-ion induced central collisions.
The technological progress of electronic devices is still enormous. Modern electronic devices already reached nanometer dimensions. Simultaneously, the computing power of these devices increases. This development implies enhancing power and heat densities. The cooling of these nanostructured devices is a challenging task of great interest. A fundamental understanding of heat transport on the nanoscale is necessary for optimizing thermal management. For a better understanding of thermal transport on the nanoscale, systematic investigations of structure-property relationships are required. For this purpose, model systems with precise structural and chemical control are essential.
However, such nanostructured materials usually provide only small sample geometries. The small dimensions make thermal conductivity characterization quite challenging. For this work, a photoacoustic (PA) setup was implemented. With this method, it is possible to characterize thin films of a sample, which is supported by a substrate. Thus, small amounts of brittle samples that cannot be processed into freestanding films can be characterized. The capability of the PA method to determine the thermal properties of thin films was demonstrated by the investigation of three different polymer-based materials.
The first two materials present the class of polymer nanocomposites (PNCs). Due to the miscibility on the molecular level, these can be also referred to as hybrid materials. The investigated PNCs can be divided by their filler geometry. First, the most straightforward filler geometry is investigated. Spherical Ag nanoparticles (NPs) are functionalized by polystyrene (PS) brushes of different molecular weights. The steric repulsion allows the adjustment of the interparticle distance (IPD) from 2 nm to 16 nm in the resulting PNC material. The ligand exchange used for this purpose is designed to be flexible. Thus, also different material combinations are viable with the presented procedure. Additionally, a new purification method is introduced, the centrifugation at θ-conditions of the ligand.
The AgPS PNCs were processed into thin films and characterized regarding optical, mechanical and thermal properties. The individual distribution of the Ag NPs preserves the localized surface plasmon resonance (LSPR). Therefore, a laser can be used to locally heat up the sample within the laser spot. The higher the Ag volume fraction, the more significant the thermoplasmonic effect. Also the mechanical properties, determined by Brillouin light scattering (BLS) measurements, and the thermal conductivity depend on the Ag ratio. However, thermal conductivity could not be predicted by effective medium models without an finite interfacial thermal conductance. Accordingly, our findings suggest, that interfaces have an impact on thermal conductivity in this nanostructured material.
The second filler type is characterized by two-dimensional extensions. The in-plane dimensions of these sheets are in the micrometer regime, while their thickness in cross-plane…