Electronic effects of heterocyclic ring systems as evaluated with the aid of 13C and 15N NMR chemical shifts and NBO analysis

The electronic effects of the 5‐ and 6‐membered heterocyclic rings on the C?N? N unit of five different hydrazone derivatives of pyridine‐2‐, ‐3‐ and ‐4‐carbaldehydes, pyrrole‐2‐carbaldehyde, furan‐2‐ and ‐3‐carbaldehydes and thiophene‐2‐ and ‐3‐carbaldehydes have been studied with the aid of ¹³C and ¹⁵N NMR measurements together with the natural bond orbital (NBO) analysis. As model compounds are used the corresponding substituted benzaldehyde derivatives. The polarization of the C?N unit of the hydrazone functionality of the heteroaryl derivatives occurs in an analogous manner with that of phenyl derivatives. The electron‐withdrawing heteroaryl groups destabilize and the electron‐donating groups stabilize the positive charge development at the C?N carbon while the effect on the negative charge development is opposite. The ¹⁵N NMR chemical shift of the C?N and C?N? N nitrogens and the NBO charges at C?N? N unit can be correlated with the replacement substituent constants σ of the heteroaryl groups. ¹³C NMR shifts of the C?N carbon of N,N‐dialkylhydrazones of the heteroarenecarbaldehydes can be correlated with a dual parameter equation possessing the polar substituent constant σ* of the heteroaryl group and the electronegativity of the heteroatom as variables. Copyright © 2008 John Wiley & Sons, Ltd.     

Strongly confined semiconductor quantum dots: Pair excitations and optical properties

This paper reviews a microscopic model of basic electron-hole pair excitation processes in strongly confined semiconductor quantum dots (QD) and their influence on the optical QD properties. The effects of valence band mixing, Coulomb interaction, and surface polarization are taken into account. The exciton and biexciton wave functions and energies are obtained using a numerical diagonalization method. The computed optical spectra, such as absorption, gain, pump-probe, and two-photon absorption, agree well with experiments.     

Untersuchungen zur anwendung ternärer komplexe in der photometrie—III: Die bestimmung des titanium(iv) mit brompyrogallolrot in gegenwart von nitrilotriessigsäure bzw. ethylenediamintetraessigsäure

As part of a continued investigation of the analytical applications of ternary complexes, the systems Ti(IV)/BPR, I), Ti(IV)/BPR/EDTA (II), and Ti(IV)/BPR/NTA (III), where BPR = Bromopyrogallol Red, have been investigated and compared in terms of working concentration range, molar absorptivity, standard deviation, coefficient of variation, calibration sensitivity, limit of detection and of determination. A novel way of summarizing the effects of interferences of a large group of ions (some 47 in all) is presented. The results show that the ternary systems, in particular system II, have a better selectivity than the simple binary system I of titanium with Bromopyrogallol Red.     

Electronic band structure of solid CO2 as determined from the hv-dependence of photoelectron emission

Photoelectron energy distribution curves from solid CO₂ have been determined for excitation energies from hv = 14 up to 40 eV using synchrotron radiation. A 1:1 correspondence to the gas-phase photoelectron spectrum is observed for the occupied molecular orbitals. The vertical binding energies E_B^v (E_VAC = 0) and widths (fwhm) of the valence bands of solid CO₂ are determined to be 13.0 and 0.95 eV (1π_g); 16.7 and 1.1 eV (1π_u); 17.6 and 0.85 eV (3σ_u) and 18.8 and 0.8 eV (4σ_g) for the individual bands respectively. The partial photoemission cross sections differ importantly from those of the gas phase in exhibiting pronounced maxima at 5.2 eV (1π_g), 4.4–5.3 eV (1π_u + 3σ_u) and 4.2 eV (4σ_g) above the vacuum level, which is attributed to effects of high density of final (conduction-band) states. Further weaker maxima are observed at higher photon energies. Contrary to the case for the gas phase, the resonances are unperturbed in the solid by degenerate autoionizing molecular Rydberg states. The molecular origin of the resonances in the continuum is discussed and related to X-ray absorption spectra, electron-scattering data and to theoretical cross-section calculations. It is shown that the same set of resonances is observed in the different experiments. The resonances occur however at different energies due to different Coulomb interactions. The photoemission results presented provide also a key to the hitherto unexplained optical spectrum of solid CO₂ in the VUV range, making possible an assignment of the structures observed to Frenkel-type excitons (hv ≤ 15 eV) and interband transitions (hv ? 15 eV).     

Initial State Interaction in the (π+,3p) Reaction on N, Ar and Xe

The pion absorption reaction (π^{+,3 p} ) on Ar was studied at pion energies of 70, 118, 162 and 239 MeV, and on N and Xe at 239 MeV. The 3p cross section with a 50 MeV cut on the missing energy is presented. The existence of an initial state interaction (ISI) component to the reaction was investigated. The portion of the 3p cross section assigned to the ISI process is less than one half and at lower energies significantly so. Received: 11 December 1997     

Comparison of CEPA and CP-MET methods

The known CEPA variants CEPA (v) withv = 0,1,2,3 and two new ones withv = 4, 5 are compared both formally and for various numerical examples with CP-MET. The main conclusions are: 1. In those situations where both CP-MET and the CEPA variants are justified (i.e. for “good” closed shell states) the correlation energies obtained with the 7 different schemes differ very little (by something like ±2%), with CEPA (1) closest to CP-MET (difference usually a fraction of 1%) and CEPA (4) nearly as close; this is rather insensitive to whether one uses canonical or localized orbitals. Even CEPA (3) is not too far from CP-MET, which confirms an earlier suggestion of Kelly. 2. In those cases where one of the 7 schemes fails (e.g. due to near degeneracy as in covalent molecules at large internuclear distances) the other 6 usually fail as well, though CEPA (0) is then somewhat poorer than the other schemes. Then no longer CEPA (1) but rather CEPA (3) is closest to CP-MET and then all schemes converge much better in a localized representation. 3. CEPA (2) usually leads to best agreement with experiment since it simulates to some extent triple substitutions. In none of the studied examples does CP-MET show a significant superiority as compared to the other schemes. Possible improvements to extend the domain of applicability of these methods are discussed.     

Collective and two-quasiparticle states in 158Gd observed through study of radiative neutron capture in 157Gd

The level structure of ¹⁵⁸Gd has been studied using the prompt γ-rays and conversion electrons emitted following neutron capture in ¹⁵⁷Gd. The γ-ray energy and intensity measurements were made using both Ge(Li) detectors and a curved-crystal spectrometer. Conversion-electron energy and intensity measurements were made using two separate magnetic spectrometers: one to measure the primary electron spectrum and the other to measure the lower energy secondary electron spectrum. Some γ-γ coincidence measurements were also made among the secondary γ-rays. From these data, a neutron separation energy of 7937.1 ± 0.5 keV has been determined for ¹⁵⁸Gd. A level scheme containing 59 excited states with energies < 2.25 MeV, for which de-excitation modes have been identified, is proposed for ¹⁵⁸Gd. Many of these states have been grouped into rotational bands. A total of thirteen excited rotational bands with band-head energies below 2.0 MeV are contained in the level scheme. Features of the proposed level scheme include: the K^π = 0^?, 1^? and 2^? octupole-vibrational bands with band-head energies of 1263, 977 and 1793 keV, respectively; the γ-vibrational band at 1187 keV; three excited K^π = 0⁺ bands with band-head energies of 1196, 1452 and 1743 keV; several two-quasiparticle bands with band-head energies in keV (and K^π assignments) of 1380 (4⁺), 1636 (4^?), 1847 (1⁺), 1856 (1^?), 1920 (4⁺) and 1930 (1⁺). An analysis of (d, p) reaction data is presented which permits definite two-quasiparticle configuration assignments to be made to most of these latter bands. Evidence is presented which suggests strong mixing of some two-neutron and two-proton bands. A phenomenological four-band mixing analysis is made of the energy and E2 transition-probability data for the ground-state band and the three lowest-lying excited collective positive-parity bands. Good agreement with experiment is obtained. A Coriolis-mixing analysis of the octupole bands has been carried out and good agreement with the data on level energies and E1 transition probabilities to the ground-state band has been achieved. Values of Z, the ratio of the E1 transition matrix element with ΔK = 1 to that with ΔK = 0, involving the octupole bands and the first four 0⁺ bands are derived. For three of these 0⁺ bands, absolute values of these matrix elements are deduced. An interesting alternation in the sign of Z is observed for these four 0⁺ bands.     

Application of artificial intelligence for the determination of reaction mechanisms

TA curves can be interpreted kinetically by pattern recognition. Readily available symbol strings are compared with those of theoretical curves, stored in a data bank. Such kinetic codes fix the dependences of the mechanistic coordinates on the initial concentration ofone of the reactants; obviously, they are scarcely influenced by the prevailing values of the activation parameters.The foundations for a model-determinating computer program and the experiences with its application are presented. The program reveals the possible homogeneous two-reaction models from an experimental DTA- or non-isothermal UV-series; these are listed in the order of their evidence values. Similarly, the best superpositions of two two-reaction models are determined.

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Zusammenfassung Ein kinetisches Auswerteverfahren wird beschrieben, das für jedes homogene System, welches einer thermoanalytischen Messung bei konstanter Heizrate unterworfen werden kann, eine Liste der wahrscheinlichsten Ein- bis Vierstufenmodelle ausgibt, Aus der Konzentrationsabhängigkeit der mechanistischen Koordinaten (korrigierter Formfaktor und Reaktionstypindex) werden charakteristische Zeichenketten erhalten und in einem Mustererkennungsverfahren mit den analog berechneten Zeichenketten aus den Konzentrationssätzen aller denkbaren Modelle verglichen.

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