On the ion beam stopping power dependence of transient magnetic fields in Fe- and Gd-hosts

Ion-beam induced attenuations of transient magnetic fields have been further studied in measurements on high-velocity²⁴Mg- and²⁸Si-ions as well as low-velocity⁴⁸Ti-ions using energetic beams of Ti- and Br-ions. Further evidence for the stopping power dependence of the attenuations is found; more data in the threshold region of Fe-host support earlier observations. In Gd-host the attenuations are again weaker pronounced than in Fe in accordance with previous data.     

Evidence for genotoxic effects of resonant ELF magnetic fields

The possibility that extremely low frequency (ELF) magnetic fields affect the genomic integrity of the cell is the objective of this study. Human peripheral lymphocytes (HPLs) were exposed to different exposure conditions combining ac and static magnetic fields. We used the micronuclei (MN) cytogenetic technique, because MN formation is considered as a marker of chromosomal damage produced by genotoxic agents.The first set of experiments were performed at 50 Hz, 150 μT rms and 32 Hz, 75 μT and 150 μT rms magnetic fields with the static geomagnetic field components nulled. No effects were detected using the MN test on HPL as an indicator for cellular genomic damage when the static magnetic field was nulled. Moreover, such exposure to an ac magnetic field does not appear to interfere with the action of a powerful genotoxic agent mytomicin-C (MMC), i.e. there was no synergistic effect.The second set of experiments were conducted exposing cells to 32 Hz, 150 μT and 75 μT rms, parallel to a 42 μT dc magnetic field. The 75 μT rms, 32 Hz exposure condition was chosen to maximize the resonance effect on Ca²⁺ according to parametric resonance theory. We found a statistically significant increase of MN for both exposure conditions. This experiment provides evidence for the genotoxic effects of resonant ELF magnetic fields in human lymphocytes.     

Canonical orbital contributions to the magnetic fields induced by global and local diatropic and paratropic ring currents

The induced magnetic field (IMF) of naphthalene, biphenyl, biphenylene, benzocyclobutadiene, and pentalene is dissected to contributions from the total π system, canonical π‐molecular orbitals (CMO), and HOMO→π* excitations, to evaluate and interpret relative global and local diatropicity and paratropicity. Maps of the IMF of the total π system reveal its relative strength and topology that corresponds to global and local diatropic and paratropic ring currents. The total π magnetic response is determined by this of canonical HOMOs and particularly by paratropic contributions of rotational excitations from HOMOs to unoccupied π * orbitals. Low energy excitations and similar nodal structure of HOMO and π * induce strong paratropic fields that dominate on antiaromatic rings. High energy excitations and different nodal structures lead to weak paratropic contributions of canonical HOMOs, which are overwhelmed by diatropic response of lower energy canonical orbitals in aromatic rings. CMO‐IMF analysis is found in agreement with ring current analysis. © 2017 Wiley Periodicals, Inc.     

Edges of two-dimensional electron systems under strong magnetic fields

Two-dimensional electron systems, which exist e.g. at interlaces between two different semiconductors, exhibit interesting physical properties under strong magnetic fields. In interpreting the quantum Hall effect the role of one-dimensional system edges begins to be taken into account.

The electron structure, connected with Landau quantization of 2D electron states under magnetic field, has been studied in the vicinity of system edges. Model systems with abrupt confinement barriers exhibit electron dispersions with edge plateaus above the barrier tops, accompanied by regions of substantially reduced gaps between neighbouring Landau branches. Selfconsistent results for smoothly confined systems provide alternating channels of compressible and incompressible Fermi liquids along the system edges. Recent investigation illustrates the transition between the two limiting confinement barrier cases.

In order to evaluate the Hall conductivity, the Kubo formula has been adopted in a straightforward manner to two-dimensional stripes confined by arbitrary barriers. Total deviation of the Hall conductivity from the integer values is given by the product of two factors: the geometrical factor is inversely proportional to the sample width and the edge factor is proportional to the derivative of the electron dispersion at the Fermi level and is thus governed by the shape of the confinement barrier. The deviations have been evaluated for model systems of various widths and a qualitative agreement with recent experimental data for quantum wires has been found.

The formulas provide also current densities and this enables to investigate spatial distributions of the electron current across the Hall stripes. Application to the abruptly confined model shows that the quantized part of the total current takes place within the interior of the stripe whereas the edge currents distribution is affected by the confinement barrier.     

Surface chirality effects induced by magnetic fields

Symmetry breaking in magnetohydrodynamic vortices induces surface chirality on electrodeposit films.

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Evidence for through-space electron transfer in the distance dependence of normal and inverted electron transfer in oligoproline arrays

Four new helical oligoproline assemblies containing 16, 17, 18, and 19 proline residues and ordered arrays of a Ru(II)-bipyridyl chromophore and a phenothiazine electron-transfer donor have been synthesized in a modular fashion by solid-phase peptide synthesis. These arrays are illustrated and abbreviated as CH(3)CO-Pro(6)-Pra(PTZ)-Pro(n)()-Pra(Ru(II)b(2)m)(2+)-Pro(6)-NH(2), where PTZ is 3-(10H-phenothiazine-10)propanoyl and (Ru(II)b'(2)m)(2+) is bis(4,4'-diethylamide-2,2'-bipyridine)(4-methyl,4'-carboxylate,2,2'-bipyridine)ruthenium(II) dication with n = 2 (2), 3 (3), 4 (4), and 5 (5). They contain PTZ as an electron-transfer donor and (Ru(II)b'(2)m)(2+) as a metal-to-ligand charge transfer (MLCT) light absorber and are separated by proline-to-proline through-space distances ranging from 0 (n = 2) to 12.9 A (n = 5) relative to the n = 2 case. They exist in the proline-II helix form in water, as shown by circular dichroism measurements. Following laser flash Ru(II) --> b'(2)m MLCT excitation at 460 nm in water, excited-state PTZ --> Ru(2+) quenching (k(2)) occurs by reductive electron transfer, followed by Ru(+) --> PTZ(+) back electron transfer (k(3)), as shown by transient absorption and emission measurements in water at 25 degrees C. Quenching with DeltaG degrees = -0.1 eV is an activated process, while back electron transfer occurs in the inverted region, DeltaG degrees = -1.8 eV, and is activationless, as shown by temperature dependence measurements. Coincidentally, both reactions have comparable distance dependences, with k(2)( )()varying from = 1.9 x 10(9) (n = 2) to 2.2 x 10(6) s(-)(1) (n = 4) and k(3) from approximately 2.0 x 10(9) (n = 2) to 2.2 x 10(6) s(-)(1) (n = 4). For both series there is a rate constant enhancement of approximately 10 for n = 5 compared to n = 4 and a linear decrease in ln k with the through-space separation distance, pointing to a significant and probably dominant through-space component to intrahelical electron transfer.     

Investigations on the kinetics of electron transfer reactions in magnetic fields

There is a controversial debate if a magnetic field can influence the rate of electron transfer (ET) reactions. In this paper, we report kinetic measurements of the ET rate constants for the redox couples [IrCl6]2-/[IrCl6]3-, [Fe(CN)6]3-/[Fe(CN)6]4-, and [Fe(H2O)6]3+/[Fe(H2O)6]2+ in magnetic fields up to 1 T. To reduce effects arising from magnetically induced mass transport (magnetohydrodynamic effect), disk microelectrodes with a diameter of 50 microm were used in potentiodynamic (cyclic and linear sweep voltammetry) and in electrochemical impedance spectroscopy experiments. None of the investigated redox couples showed a magnetic field effect on the ET rate constant.     

A stochastic model for transient magnetic fields as observed by perturbed angular distribution of gamma rays

A stochastic model is introduced to study the transient magnetic field (TF) experienced by the nuclei of fast ions traversing a ferromagnetic medium. The field is assumed to arise primarily from the bound electrons of the ion, polarized by the internal magnetic field of the ferromagnetic specimen. Spin-flip scattering is considered to be the dominant mechanism for polarization transfer from the host to the ion. Electron capture and loss mechanisms are also taken into account in a phenomenological manner. An analytical expression is derived for the TF which depends on the electron capture and loss cross-sections. The result for the perturbation factor is shown to be more general than that derived by Abragam and Pound and reduces to their result in the appropriate limit.     

Strong enhancement of transient magnetic fields in Gd over Fe for oxygen ions at high velocities

Precision data on transient magnetic fields (TF) in ferromagnetic Gd and Fe were obtained for oxygen ions at velocities between 2 and 8v ₀ (v ₀=c/137) using the¹⁶O(3^?) state as probe. At the high velocities the TF in Gd were found to be twice as large as in Fe which is in contrast to the generally observed scaling with the polarization density of the hosts. Degrees of polarization could be deduced from TF strengths using measured ion fractions of singly occupiedK-shell. The values derived were compared with theoretical estimates based on spin exchange scattering as a possible polarization mechanism.     

Spin exchange scattering as the most likely polarization mechanism in transient magnetic fields

Salient features of transient magnetic fields, like the degree of polarization, host dependence etc. emerging from studies of high velocity single-electron light ions,Z ≦ 16, are well described by spin exchange scattering as the polarization transfer mechanism. Inclusion of density enhancement effects of the electrons of the solid in the Coulomb field of the moving ion are necessary for a quantitative understanding of the observed large degrees of polarization of the ions.     

Transient oxygen clathrate-like hydrate and water networks induced by magnetic fields

Recently, careful experiments of oxygen-dissolved pure water treated by high magnetic fields showed indirectly the existence of magnetic field-affecting water (MFA water), which brought about a decrease in the contact angle of water on metals, an increase in the electrolytic potential of water, inhibition of metal corrosion, and changes in the crystal structure of calcium carbonate due to magnetic treatment. Here we report the infrared and Raman spectroscopic evidence indicating quasi-stable structures in the MFA water; oxygen clathrate-like hydrate and developed water networks, which were induced by magnetic interactions while a vacuum-distilled water, followed by oxygen exposure, crossed a steady magnetic field. The mechanism of MFA water formation and survival under thermal fluctuation is a challenging problem for the science community.     

Quantitative theory of chemically induced dynamic nuclear polarisation in high magnetic fields

Further development of the diffusional model of the radical pair is suggested. A function is proposed for the exponential distribution of the diffusional trajectories of the radicals in a radical pair. By this function, the differences in the populations of nuclear spin levels in the molecules are calculated for the S, T and U precursor pairs. The equations which express the relationship between the theoretically calculated population differences and the experimentally determined enhancement coefficients are derived.     

Evidence for an aryl migration during the electron impact induced fragmentation of substituted aryloxymethylquinoxalines.

The electron impact (EI) mass spectra of 34 differently substituted 2-phenoxymethyl-, 2-naphthyloxymethyl-, 2-pyridinyloxymethyl- and 2-chinolinyloxymethylquinoxalines were recorded. The fragmentation patterns were examined by metastable ion analysis and exact mass measurements, employing finally also selective deuterium labelling. The inclusion of the substituted aryl ring moiety appears to be important for the fragmentation of the aryloxymethylquinoxalines. A molecular ion rearrangement is proposed for the observed loss of OH* and CHO* radicals. The influence of the different substituents on the aryl ring moiety on the rearrangement in the gas phase and on the resulting fragmentation was investigated.     

Dyson-corrected orbital energies for the perturbative treatment of electron correlation

The effect of replacing the Hartree–Fock one-particle energies with ionization potentials obtained from inverse Dyson equation when calculating electron correlation energies perturbatively is investigated. Though the energy shifts vary from system to system, the slight decrease of the resulting excitation energies at around equilibrium geometries leads to a slight increase of the correlation energies in most cases. In the dissociation limit the inverse Dyson equation opens the gap, thus nondiverging potential curves emerge even at the restricted Hartree–Fock (RHF)+RS2 level. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 713–719, 1998     

Chemically induced electron spin polarization: The dependence on radical concentration and structure

Enhancement factors (V_q) from electron spin resonance spectra of the emission-absorption type have been shown to depend on radical concentration and also on radical structure. The relative V_q's of a spectrum could be satisfactorally calculated from the theory of Adrian.     

Advances in detection of magnetic fields induced by electrochemical reactions—a review

The paper summarizes achievements in applications of superconducting quantum interference device (SQUID) magnetometry in electrochemical activity sensing, especially in that related to remote corrosion detection. The studies deal with application of the SQUIDs operating in liquid helium or nitrogen with a spatial resolution of magnetic field detection of the order of a millimeter or greater. This made it possible to observe macroscopic magnetic fields, which originated from the large-scale surface currents (ionic and electronic), which resulted from electrochemical potential gradients on electrochemical interfaces. The gradients owed to variations in temperature, alloy composition, sample geometry, electrolyte flow characteristics (velocity, direction, and turbulence), etc. The measurements demonstrated the capability of SQUIDs to remotely sense corrosion across the integrated media consisting of gaseous and solid dielectrics, metal, and electrolyte. The results have shown the potential of magnetometry for practical corrosion detection in the restricted locations such as in ground or concrete. Despite significant efforts, the field is considered to be at an early stage from both fundamental and practical points of view. Contribution to special issue “Magnetic field effects in Electrochemistry”.     

Molecular orbital theory of electron donor-acceptor complexes

A Gaussian basis set consisting of 12s-type, 6p-type and 4d-type functions has been optimized for the third row atoms, together with a 9s, 5p, 3d set for the corresponding dipositive ion. The applicability of these atomic sets for molecular calculation is discussed.

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Zusammenfassung Ein Basissatz von 12s-, 6p- und 4d-Funktionen für die Atome der dritten Reihe des periodischen Systems ist optimalisiert worden; das gleiche gilt für einen entsprechenden Satz für die zweifach positiven Ionen aus 9s-, 5p- und 3d-Funktionen. Ferner wird ihre Anwendbarkeit bei Rechnungen an Molekülen diskutiert.

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Résumé On présente un ensemble optimal de fonctions de base gaussiennes pour les atomes et les ions de la troisième ligne. Cet ensemble est constitué de 12 fonctions du type s, 6 fonctions du type p et 4 fonctions du type d pour l'atome neutre et de 9 fonctions s, 5 fonctions p et 3 fonctions d pour l'ion M²⁺. On discute l'emploi de ces bases pour des calculs moléculaires.

     

Longitudinal electron spin relaxation induced by degenerate electron exchange as studied by time-resolved magnetic field effects

T(1) paramagnetic relaxation of radical ions induced by degenerate electron exchange (DEE) reactions is studied theoretically and experimentally. Our theoretical analysis shows that T(1) relaxation time is well described by the Redfield theory at arbitrary values of the characteristic DEE time tau. Longitudinal relaxation of norbornane (NB) radical cation is studied by means of the time-resolved magnetic field effects (TR-MFE) technique; the rate constant of DEE involving NB(*+) radical cation and NB neutral molecule is obtained. Advantages of the TR-MFE technique and its potential for measuring the short DEE times are discussed in detail.