Polychlorinated trityl radicals for dynamic nuclear polarization: the role of chlorine nuclei

Polychlorinated trityl radicals bearing carboxylate substituents are water soluble persistent radicals that can be used for dynamic nuclear polarization. In contrast to other trityl radicals, the polarization mechanism differs from the classical solid effect. DFT calculations performed to rationalize this behaviour support the hypothesis that polarization is transferred from the unpaired electron to chlorine nuclei and from these to carbon by spin diffusion. The marked differences observed between neutral and anionic forms of the radical will be discussed.

Magnetism of isolated Mn12 single-molecule magnets detected by magnetic circular dichroism: Observation of spin tunneling with a magneto-optical technique

We report magnetic and magneto-optical measurements of two Mn12 single-molecule magnet derivatives isolated in organic glasses. Field-dependent magnetic circular dichroism (MCD) intensity curves (hysteresis cycles) are found to be essentially identical to superconducting quantum interference device magnetization results and provide experimental evidence for the potential of the optical technique for magnetic characterization. Optical observation of magnetic tunneling has been achieved by studying the decay of the MCD signal at weak applied magnetic field

Assessing technology-based spin-offs from university support units

This paper takes a regional studies approach to assess spin-offs from a university-based technology transfer network. We first detect the regional objectives, inputs and outputs needed to assess spin-offs from support programmes. We then provide evidence on regional mechanisms for firm creation. We analyse spin-offs created at Catalan universities and find that many efficient spin-offs have formal technology transfer agreements, and emerge from technology-oriented universities. We also find that higher innovation levels and experience from the parent university are associated with higher efficiency, which is positively related to future fundamental profitability. Finally, we propose regional policy making and research directions.

Controlling the spin of metal atoms adsorbed on oxide surfaces: Ni on regular and defective sites of the MgO(001) surface

We have analyzed the relative energy of nonmagnetic and magnetic low-lying electronic states of Ni atoms adsorbed on regular and defective sites of the MgO(001) surface. To this end cluster and periodic surface models are used within density functional theory. For Ni atoms adsorbed on oxygen vacancies at low coverage, the interaction energy between the metal and the support is much larger than on regular sites. Strong bonding results in a diamagnetic adsorbed species and the energy required to reach the high-spin state increases. Moreover, a correlation appears between the low-spin to high-spin energy difference and the interaction energy hypothesizing that it is possible to prepare the surface to tune the high-spin to low-spin energy difference. Magnetic properties of adsorbed thin films obtained upon increasing coverage are more difficult to interpret. This is because the metallic bond is readily formed and dominates over the effect of the atoms directly bound to the vacancy.

Correlation of the EPR properties of perchlorotriphenylmethyl radical and their efficiency as DNP polarizers

Water soluble perchlorinated trityl (PTM) radicals were found to be effective 95 GHz DNP (dynamic nuclear polarization) polarizers in ex situ (dissolution) 13C DNP (Gabellieri et al., Angew Chem., Int. Ed. 2010, 49, 3360). The degree of the nuclear polarization obtained was reported to be dependent on the position of the chlorine substituents on the trityl skeleton. In addition, on the basis of the DNP frequency sweeps it was suggested that the 13C NMR signal enhancement is mediated by the Cl nuclei. To understand the DNP mechanism of the PTM radicals we have explored the 95 GHz EPR characteristics of these radicals that are relevant to their performance as DNP polarizers. The EPR spectra of the radicals revealed axially symmetric g-tensors. A comparison of the spectra with the 13C DNP frequency sweeps showed that although the solid effect mechanism is operational the DNP frequency sweeps reveal some extra width suggesting that contributions from EPR forbidden transitions involving 35,37Cl nuclear flips are likely. This was substantiated experimentally by ELDOR (electron-electron double resonance) detected NMR measurements, which map the EPR forbidden transitions, and ELDOR experiments that follow the depolarization of the electron spin upon irradiation of the forbidden EPR transitions. DFT (density functional theory) calculations helped to assign the observed transitions and provided the relevant spin Hamiltonian parameters. These results show that the 35,37Cl hyperfine and nuclear quadrupolar interactions cause a considerable nuclear state mixing at 95 GHz thus facilitating the polarization of the Cl nuclei upon microwave irradiation. Overlap of Cl nuclear frequencies and the 13C Larmor frequency further facilitates the polarization of the 13C nuclei by spin diffusion. Calculation of the 13C DNP frequency sweep based on the Cl nuclear polarization showed that it does lead to an increase in the width of the spectra, improving the agreement with the experimental sweeps, thus supporting the existence of a new heteronuclear assisted DNP mechanism.

Nuclear surface properties in relativistic effective field theory

We perform Hartree calculations of symmetric and asymmetric semi-infinite nuclear matter in the framework of relativistic models based on effective hadronic field theories as recently proposed in the literature. In addition to the conventional cubic and quartic scalar self-interactions, the extended models incorporate a quartic vector self-interaction, scalar-vector non-linearities and tensor couplings of the vector mesons. We investigate the implications of these terms on nuclear surface properties such as the surface energy coefficient, surface thickness, surface stiffness coefficient, neutron skin thickness and the spin-orbit force.

Ferromagnetism in transparent thin films of MgO

We show both theoretical and experimental evidences of the appearance of ferromagnetism in MgO thin films. First-principles calculations allow predicting the possibility of the formation of a local moment in MgO, provided the existence of Mg vacancies which create holes on acceptor levels near the O 2p-dominated valence band. Magnetic measurements evidence of the existence of room-temperature ferromagnetism in MgO thin films. High-resolution transmission electron microscopy demonstrates the existence of cation vacancies in our samples. Finally, by applying the element specificity of the x-ray magnetic circular dichroism technique, we also demonstrate that the magnetic moments of the system arise from the spin polarization of the 2p electrons of oxygen atoms surrounding Mg vacancies.

Antireflection coatings from analogy between electron scattering and spin precession

We use the analogy between scattering of a wave from a potential, and the precession of a spin-half particle in a magnetic field, to gain insight into the design of an antireflection coating for electrons in a semiconductor superlattice. It is shown that the classic recipes derived for optics are generally not applicable due to the different dispersion law for electrons. Using the stability conditions we show that a Poisson distribution of impedance steps is a better approximation than is a Gaussian distribution. Examples are given of filters with average transmissivity exceeding 95% over an allowed band.

Fast generation of spin-squeezed states in bosonic Josephson junctions

We describe methods for the fast production of highly coherent-spin-squeezed many-body states in bosonic Josephson junctions. We start from the known mapping of the two-site Bose-Hubbard (BH) Hamiltonian to that of a single effective particle evolving according to a Schrödinger-like equation in Fock space. Since, for repulsive interactions, the effective potential in Fock space is nearly parabolic, we extend recently derived protocols for shortcuts to adiabatic evolution in harmonic potentials to the many-body BH Hamiltonian. A comparison with current experiments shows that our methods allow for an important reduction in the preparation times of highly squeezed spin states.

The summer North Atlantic Oscillation in CMIP3 models and related uncertainties in projected summer drying in Europe

This paper discusses uncertainties in model projections of summer drying in the Euro-Mediterranean region related to errors and uncertainties in the simulation of the summer NAO (SNAO). The SNAO is the leading mode of summer SLP variability in the North Atlantic/European sector and modulates precipitation not only in the vicinity of the SLP dipole (northwest Europe) but also in the Mediterranean region. An analysis of CMIP3 models is conducted to determine the extent to which models reproduce the signature of the SNAO and its impact on precipitation and to assess the role of the SNAO in the projected precipitation reductions. Most models correctly simulate the spatial pattern of the SNAO and the dry anomalies in northwest Europe that accompany the positive phase. The models also capture the concurrent wet conditions in the Mediterranean, but the amplitude of this signal is too weak, especially in the east. This error is related to the poor simulation of the upper-level circulation response to a positive SNAO, namely the observed trough over the Balkans that creates potential instability and favors precipitation. The SNAO is generally projected to trend upwards in CMIP3 models, leading to a consistent signal of precipitation reduction in NW Europe, but the intensity of the trend varies greatly across models, resulting in large uncertainties in the magnitude of the projected drying. In the Mediterranean, because the simulated influence of the SNAO is too weak, no precipitation increase occurs even in the presence of a strong SNAO trend, reducing confidence in these projections.