Nuclear relaxation in dynamic nuclear polarization

The behavior of nuclear polarization in a substance, i.e., a solution of the complex HMBA(Cr^V)Na⁺ in 1,2-propylene glycol used in polarized nuclear targets is experimentally investigated by magnetic spectroscopic methods under conditions of dynamic nuclear polarization at hv_S/kT=≈1.5−3.2. Nuclear polarization is measured and analyzed as a function of time at different values of the saturating microwave signal and temperature. It is shown that the process of decreasing the nuclear polarization involving free nuclear relaxation is described by a nonmonoexponential law with two damping decrements, which determine the time of reaching equilibrium between the Zeeman nuclear subsystem, the dipole-dipole pool, and the lattice. Specific features of dynamic processes proceeding in the electronic-nuclear system of the substance investigated are discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 363–366, May–June, 1997.     

High-frequency dynamic nuclear polarization in the nuclear rotating frame

A proton dynamic nuclear polarization (DNP) NMR signal enhancement (epsilon) close to thermal equilibrium, epsilon = 0.89, has been obtained at high field (B(0) = 5 T, nu(epr) = 139.5 GHz) using 15 mM trityl radical in a 40:60 water/glycerol frozen solution at 11 K. The electron-nuclear polarization transfer is performed in the nuclear rotating frame with microwave irradiation during a nuclear spin-lock pulse. The growth of the signal enhancement is governed by the rotating frame nuclear spin-lattice relaxation time (T(1rho)), which is four orders of magnitude shorter than the nuclear spin-lattice relaxation time (T(1n)). Due to the rapid polarization transfer in the nuclear rotating frame the experiment can be recycled at a rate of 1/T(1rho) and is not limited by the much slower lab frame nuclear spin-lattice relaxation rate (1/T(1n)). The increased repetition rate allowed in the nuclear rotating frame provides an effective enhancement per unit time(1/2) of epsilon(t) = 197. The nuclear rotating frame-DNP experiment does not require high microwave power; significant signal enhancements were obtained with a low-power (20 mW) Gunn diode microwave source and no microwave resonant structure. The symmetric trityl radical used as the polarization source is water-soluble and has a narrow EPR linewidth of 10 G at 139.5 GHz making it an ideal polarization source for high-field DNP/NMR studies of biological systems.     

Relaxometry of insensitive nuclei: optimizing dissolution dynamic nuclear polarization

We report measurements of spin-lattice relaxation of carbon-13 as a function of the magnetic field ('relaxometry') in view of optimizing dissolution-DNP. The sample is temporarily lifted into the stray field above a high-resolution magnet using a simple and inexpensive 'shuttle'. The signals of arbitrary molecules can be observed at high field with high-resolution and sensitivity. During the dissolution process and subsequent 'voyage' from the polarizer to the NMR magnet, relaxation is accelerated by paramagnetic polarizing agents, but it can be quenched by using scavengers.     

Nuclear polarization effects in spectra of multicharged ions

We evaluate the nuclear-polarization energy shifts for one-electron ²⁰⁸₈₂Pb and ²³⁸₉₂U ions. In contrast to previous calculations, the effect of nuclear polarizability is found to be essentially of minor significance for high-precision measurements of the Lamb shift in heavy multicharged ions. The calculations are carried out employing different numerical methods. We also provide a comparison of our numerical results with analytical estimates.     

Overhauser dynamic nuclear polarization and molecular dynamics simulations using pyrroline and piperidine ring nitroxide radicals

The efficiency of Overhauser dynamic nuclear polarization (DNP) depends on the local dynamics modulating the dipolar coupling between the two interacting spins. By attaching nitroxide based spin labels to molecules and by measuring the ¹H DNP response of solvent water, information about the local hydration dynamics near the spin label can be obtained. However, there are two commonly used types of nitroxide ring structures; a pyrroline based and a piperidine based molecule. It is important to know when comparing different experiments, whether changes in DNP enhancements are due to changes in local hydration dynamics or because of the different spin label structures. In this study we investigate the key parameters affecting DNP signal enhancements for 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl, a 5-membered ring nitroxide radical, and for 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, a 6-membered ring nitroxide radical. Using X-Band DNP, field cycling relaxometry, and molecular dynamics simulations, we conclude that the key parameters affecting the DNP amplitude of the ¹H signal of water to be equal when using either nitroxide. Thus, experiments measuring hydration dynamics using either type of spin labels may be compared.     

Chain length dependence of localized vibrational modes around a soliton in trans-polyacetylene

Vibrational frequencies of finite polyacetylene with a charged soliton are calculated using the molecular orbital method. It is found that the frequency of the translational mode has a remarkable length effect and is inversely proportional to the square of chain length. The dependence is explained by regarding the soliton as a quantum particle in a one dimensional box.     

Gate control of dynamic nuclear polarization in GaAs quantum wells

Gate control of dynamic nuclear polarization under optical orientation is demonstrated in a Schottky-gated n-GaAs/AlGaAs (110) quantum well by time-resolved Kerr rotation measurements. Spin relaxation of electrons due to mechanisms other than the hyperfine interaction is effectively suppressed as the donor induced background electron density is reduced from metallic to insulating regimes. Subsequent accumulation of photoexcited electron spins dramatically enhances dynamic nuclear polarization at low magnetic field, allowing us to tune nuclear spin polarization by external gate voltages.     

Discreteness effects on non-topological kink soliton dynamics in nonlinear lattices

We show that discreteness effects which are known to exist for topological solitons exist also for non-topological kink solitons in nonlinear lattices. Extending the technique previously proposed for topological kinks we exhibit three cases where the properties of narrow kinks in nonlinear lattices are qualitatively different. Supersonic solitons in a monoatomic chain can propagate at constant speed without losing energy due to discreteness. Subsonic kinks in a monoatomic chain permanently radiate small amplitude oscillations. In a diatomic chain both supersonic and subsonic kinks lose energy due to discreteness. The characteristics of the small amplitude oscillations radiated by the kinks, when they exist, are well determined by our theoretical approach. Additional weak nonlinear effects are also described and discussed.     

Optically erasing disorder in semiconductor microcavities with dynamic nuclear polarization

The mean squared value of the photonic disorder is found to be reduced by a factor of 100 in a typical GaAs based microcavity when exposed to a circularly polarized continuous wave optical pump without any special spatial patterning. Resonant excitation of the cavity mode excites a spatially nonuniform distribution of spin-polarized electrons, which depends on the photonic disorder profile. Electrons transfer spin to nuclei via the hyperfine contact interaction, inducing a long-living Overhauser magnetic field able to modify the potential of exciton polaritons.     

Complex shape effects in nuclear rotational spectra

We study the evolution of collectivity in the structure of nuclear rotational bands based on complex quadrupole-octupole shapes. We apply an extended version of a quadrupole-octupole rotation model capable of reproducing both the low-lying states of alternating parity bands interpreted on the basis of octupole vibrations and the higher spin states considered as members of a single octupole rotational band. In such a way, the complicated odd-even staggering effects observed in light actinide nuclei are described successfully. The implemented model analysis suggests a unified mechanism in which the octupole band structure is formed as the result of the transition from an octupole vibration (soft) mode to a rotation of a shape with a stable quadrupole-octupole deformation.     

Neutron scattering by inhomogenous distribution of proton polarization produced by the dynamic nuclear polarization

The coherent neutron scattering from polarized proton clusters was observed. Clusters of polarized protons were formed in dicychrohexyl 18-crown-6 (C₂₀H₃₆D₆) molecules. The proton polarization in the molecule was produced by the dynamic nuclear polarization (DNP). The proton polarization distribution in the DNP process was also measured in propanediol. In the stationary state, no inhomogenous distribution was found.     

Cascaded dynamic eigenstates of polarization analysis for piezoelectric polarization control

We propose the cascaded dynamic eigenstates (DESs) of polarization to analyze multicomponent polarization control (PC) devices, and achieve the analytical expression of output state of polarization (SOP) as a function of voltage for piezoelectric polarization control (PPC). By measuring the DES at the output port of the device, the prestage DESs will rotate around subsequent ones. Experimental results in PPC confirm the validity of our analysis. The average error of our theoretical output SOP is 1.23 degrees, and the SOP response time is ~10 micros, which is promising to realize a quasi-open-loop high-speed PC.     

1H dynamic nuclear polarization in supercritical ethylene at 1.4 T

(1)H dynamic nuclear polarization (DNP) has been measured in supercritical ethylene in the pressure range 60-300 bar in an external field of 1.4 T. A single-cell sapphire tube was used as a high-pressure cell, and powdered 1,3-bisdiphenylene-2-phenyl allyl (BDPA) free radicals were added and distributed at the wall of the cell. At all pressures the dominant DNP mechanism was a positive Overhauser enhancement, caused by proton-electron contact interactions at the fluid/solid radical interface. The observed enhancements varied from 12 at 60 bar to 17 at 300 bar. Besides the Overhauser enhancement, small solid state and thermal mixing enhancements also were observed, indicating that part of the ethylene was adsorbed at the radical surface for a prolonged time. The impacts of the experimental conditions on the Overhauser enhancement factors are discussed, and enhancements of at least 40-60 are estimated when the EPR saturation factor and the leakage factor become maximal. These data indicate that DNP-enhanced NMR has the potential of extending the impact of NMR in research areas involving supercritical fluids.