Valence-band electronic structure of iron phthalocyanine: an experimental and theoretical photoelectron spectroscopy study

The electronic structure of iron phthalocyanine (FePc) in the valence region was examined within a joint theoretical-experimental collaboration. Particular emphasis was placed on the determination of the energy position of the Fe 3d levels in proximity of the highest occupied molecular orbital (HOMO). Photoelectron spectroscopy (PES) measurements were performed on FePc in gas phase at several photon energies in the interval between 21 and 150 eV. Significant variations of the relative intensities were observed, indicating a different elemental and atomic orbital composition of the highest lying spectral features. The electronic structure of a single FePc molecule was first computed by quantum chemical calculations by means of density functional theory (DFT). The hybrid Becke 3-parameter, Lee, Yang and Parr (B3LYP) functional and the semilocal 1996 functional of Perdew, Burke and Ernzerhof (PBE) of the generalized gradient approximation (GGA-)type, exchange-correlation functionals were used. The DFT/B3LYP calculations find that the HOMO is a doubly occupied π-type orbital formed by the carbon 2p electrons, and the HOMO-1 is a mixing of carbon 2p and iron 3d electrons. In contrast, the DFT/PBE calculations find an iron 3d contribution in the HOMO. The experimental photoelectron spectra of the valence band taken at different energies were simulated by means of the Gelius model, taking into account the atomic subshell photoionization cross sections. Moreover, calculations of the electronic structure of FePc using the GGA+U method were performed, where the strong correlations of the Fe 3d electronic states were incorporated through the Hubbard model. Through a comparison with our quantum chemical calculations we find that the best agreement with the experimental results is obtained for a U(eff) value of 5 eV.     

The methods of determination of critical micellar concentrations of the amphiphilic systems in aqueous medium

Science is the attempt to make the chaotic diversity of our sense-experience to a logically unified system of thought. A sound theoretical basis and a rational physicochemical understanding based on experimental findings lead to a proper understanding of a topic. Colloid chemistry strengthened its footing by the extensive studies on gold sols by Michael Faraday in 1850s, however, the term “colloid” was coined by Thomas Graham in 1861. Historically, the Stone Age paintings in the Lascaux cave in France and the written records of Egyptian pharaohs were produced with stabilized colloid pigments. The part of colloid science dealing with amphiphilic molecules is so diverse on its own that it is dealt in a separate branch called the “association colloid”. A key development in the study of association colloids was the observation by James McBain that the osmotic pressure of salts of alkali metal fatty acid displayed a pronounced break in the concentration beyond a specific characteristic concentration, after which the osmotic coefficient remained almost constant (Evans and Wennerstrom, 1994). McBain attributed this fact to the self-association of these molecules among themselves (McBain, 1913, McBain, 1944) in solution. Here, we are providing a molecular as well as thermodynamic approach toward the micellization process.     

Higgs Bundles and the Fourier-Mukai Transform

The Fourier-Mukai transform is extended to the context of Higgs bundles under certain conditions. Some results valid for sheaves on abelian varieties and K3 surfaces are extended to the situation of Higgs bundles. An application to the relative setting is given.1991 Mathematics Subject Classification: 14F05 18F20.     

Pseudo-effective cone of Grassmann bundles over a curve

Let \(E\) be a vector bundle over a smooth projective curve \(X\) defined over an algebraically closed field \(k\) . For any integer \(1\,\le \, r\, <\, \mathrm{rank}(E)\) , let \(\mathrm{Gr}_r(E)\,\longrightarrow \, X\) be a Grassmann bundle parametrizing all \(r\) dimensional quotients of the fibers of \(E\) . We compute the pseudo-effective cone in the real Néron–Severi group \(\mathrm{NS}(\mathrm{Gr}_r(E))_\mathbb{R }\) . We prove that this cone coincides with the nef cone in \(\mathrm{NS}(\mathrm{Gr}_r(E))_\mathbb{R }\) if and only if the vector bundle \(E\) is semistable (respectively, strongly semistable) when the characteristic of \(k\) is zero (respectively, positive). Examples are given to show that this characterization of (strong) semistability is not true for vector bundles on higher dimensional projective varieties.     

Nanoscopically resolved dynamic charge‐carrier distribution in operating interband cascade lasers

Dynamic charge carriers play a vital role in active photonic quantum/nanodevices, such as electrically pumped semiconductor lasers. Here we present a systematic experimental study of gain‐providing charge‐carrier distribution in a lasing interband cascade laser. The unique charge‐carrier distribution profile in the quantum‐well active region is quantitatively measured at nanometer scales by using a noninvasive scanning voltage microscopy technique. Experimental results clearly confirm the accumulation and spatial segregation of holes and electrons in the beating heart of the device. The measurement also shows that the charge‐carrier density is essentially clamped in the presence of stimulated emission at low temperatures. The threshold charge‐carrier density exhibits a linear but fairly weak temperature dependence, in contrast to the exponential temperature dependence of the threshold current. The experimental approach will lead to a deeper understanding of fundamental processes that govern the operation and performance of nanoelectronic devices, quantum devices and optoelectronic devices.

     

Synthesis, characterization, and study of octanuclear iron-oxo clusters containing a redox-active Fe4O4-cubane core

A one-pot synthetic procedure yields the octanuclear Fe(III) complexes Fe(8)(micro(4-)O)(4)(micro-pz(*))(12)X(40, where X = Cl and pz(*) = pyrazolate anion (pz = C(3)H(3)N(2)-) (1), 4-Cl-pz (2), and 4-Me-pz (3) or X = Br and pz(*) = pz (4). The crystal structures of complexes 1-4, determined by X-ray diffraction, show an Fe(4)O(4)-cubane core encapsulated in a shell composed of four interwoven Fe(micro-pz(*))(3)X units. Complexes 1-4 have been characterized by 1H NMR, infrared, and Raman spectroscopies. M?ssbauer spectroscopic analysis distinguishes the cubane and outer Fe(III) centers by their different isomer shift and quadrupole splitting values. Electrochemical analyses by cyclic voltammetry show four consecutive, closely spaced, reversible reduction processes for each of the four complexes. Magnetic susceptibility studies, corroborated by density functional theory calculations, reveal weak antiferromagnetic coupling among the four cubane Fe centers and strong antiferromagnetic coupling between cubane and outer Fe atoms of 1. The structural similarity between the antiferromagnetic Fe(8)(micro(4-)O)(4) core of 1-4 and the antiferromagnetic units contained in the minerals ferrihydrite and maghemite is demonstrated by X-ray and M?ssbauer data.     

A mixed-valence octanuclear iron-oxo pyrazolate: assessment of electronic delocalization by structural and spectroscopic analysis

A formally Fe(III)(7)Fe(II) complex, containing an inner Fe(4)O(4)-cubane and four peripheral Fe centers, is derived from the one-electron reduction of its Fe(III)(8) precursor. Spectroscopic analysis of the former reveals that the redox activity of this Fe(8) system is confined within its cubane core. The resulting (Fe(4)O(4))(3+)-cubane, which is valence-delocalized in the NMR, M?ssbauer, and IR spectroscopy time scales but valence-trapped in the X-ray photoelectron spectroscopy (XPS) time scale, is better described as a Robin-Day class-II system by the analysis of its near-infrared (NIR) intervalence charge transfer (IVCT) band profile.     

Symmetries and the polarized optical spectra of exciton complexes in quantum dots

A systematic and simple theoretical approach is proposed to analyze true degeneracies and polarized decay patterns of exciton complexes in semiconductor quantum dots. The results provide reliable spectral signatures for efficient symmetry characterization, and predict original features for low C(2v) and high C(3v) symmetries. Excellent agreement with single quantum dot spectroscopy of real pyramidal InGaAs/AlGaAs quantum dots grown along [111] is demonstrated. The high sensitivity of biexciton quantum states to exact high symmetry can be turned into an efficient uninvasive postgrowth selection procedure for quantum entanglement applications.