Kinetic Magnetic‐Field Effect Involving the Small Biologically Relevant Inorganic Radicals NO and O2.−

Oxidation of dihydrorhodamine 123 (DHR) to rhodamine 123 (RH) by oxoperoxonitrite (ONOO^?), formed through recombination of NO and O₂^.? radicals resulting from thermal decomposition of 3‐morpholinosydnonimine (SIN‐1) in buffered aerated aqueous solution at pH 7.6, represents a kinetic model system of the reactivity of NO and O₂^.? in biochemical systems. A magnetic‐field effect (MFE) on the yield of RH detected in this system is explored in the full range of fields between 0 and 18 T. It is found to increase in a nearly linear fashion up to a value of 5.5±1.6 % at 18 T and 23 °C (3.1±0.7 % at 40 °C). A theoretical framework to analyze the MFE in terms of the magnetic‐field‐enhanced recombination rate constant k_rec of NO and O₂^.? due to magnetic mixing of T₀ and S spin states of the radical pair by the Δg mechanism is developed, including estimation of magnetic properties (g tensor and spin relaxation times) of NO and O₂^.? in aqueous solution, and calculation of the MFE on k_rec using the theoretical formalism of Gorelik at al. The factor with which the MFE on k_rec is translated to the MFE on the yield of ONOO^? and RH is derived for various kinetic scenarios representing possible sink channels for NO and O₂^.?. With reasonable assumptions for the values of some unknown kinetic parameters, the theoretical predictions account well for the observed MFE.     

Photoemission valence band spectra and electronic density of states in copper oxides and copper based ceramic super-conductors

Photoemission valence band spectra with three different photon energies (21.2 eV, 40.8 eV, 1253.6 eV) for Cu₂O and CuO and a number of copper oxide based superconducting ceramics are investigated, namely La₂CuO₄ (LCO), Y₁Ba₂Cu₃O₇ (YBCO), Bi₂Sr₂CaCu₂O₈ (BSCCO) and Tl₂Ba₂Ca₂Cu₃O₁₀ (TBCCO). From the Cu₂O data it can be infered, that the He-II (40.8 eV) spectra give a fair representation of the density of states (DOS). In addition the agreement between the calculated density of states (DOS) and the He-II photoemission spectrum is almost perfect for Cu₂O. This agreement is worse for CuO and the other materials which all have a Cu groundstate close to a 3d ⁹ configuration indicating a large contribution of thed-d correlation energy to the excitation spectra which is absent in Cu₂O because of the filled 3d-shell. In all cases the experimental DOS atE _F is very small and only the spectra of BSCCO show a well defined Fermi edge. The relevance of these findings with respect to the theoretical local functional density DOS calculations is discussed.     

The electronic structure of KMnO4 investigated by resonant photoemission

The valence band of potassium permanganate (KMnO₄) was investigated by means of resonant photoemission spectroscopy (ResPES) at the Mn2p, Mn3p and O1s edge. These data confirm the previous conclusions of a strong deviation from a purely ionic charge distribution in this compound. The ResPES data are in agreement with previous results about the character of the individual valence band states. A simple cluster model is used to explain qualitatively the different structures seen in the valence band spectra and their dependence on the photon energy.     

Spectroscopic and structural evidence for the hydrogen bond nature of CC---H…C=C contacts in ethynyl steroids

Structural and IR-spectroscopic evidence is given that directed contacts from terminal alkynes to C=C double bonds possess the essential characteristics of weak hydrogen bonds. The contacts are directed at the center of the π-bond rather than at one of the individual C-atoms. The contact distances from H to the center of the C=C bond are typically 2.8 Å, with the shortest distances being 2.5 Å. The interaction is of pronounced long-range nature and can be detected in the infrared spectrum even with a long H…π distance of almost 3.0 Å. The sample used is mainly composed of ethynyl steroids belonging to the progestine family.