Abstract:
There has been much renewed interest in dynamic nuclear polarization (DNP), particularly in the context of solid state biomolecular NMR and more recently dissolution DNP techniques for liquids. This paper reviews the role of spin diffusion in polarizing nuclear spins and discusses the role of the spin diffusion barrier, before going on to discuss some recent results.

Abstract:
Magnetic-field and microwave-frequency modulated DNP experiments have been shown to yield improved enhancements over conventional DNP techniques, and even to shorten polarization build-up times. The resulting increase in signal-to-noise ratios can lead to significantly shorter acquisition times in signal-limited multi-dimensional NMR experiments and pave the way to the study of even smaller sample volumes. In this paper we describe the design and performance of a broadband system for microwave frequency- and amplitude-modulated DNP that has been engineered to minimize both microwave and thermal losses during operation at liquid helium temperatures. The system incorporates a flexible source that can generate arbitrary waveforms at 94 GHz with a bandwidth greater than 1 GHz, as well as a probe that efficiently transmits the millimeter waves from room temperature outside the magnet to a cryogenic environment inside the magnet. Using a thin-walled brass tube as an overmoded waveguide to transmit a hybrid HE11 mode, it is possible to limit the losses to 1 dB across a 2 GHz bandwidth. The loss is dominated by the presence of a quartz window used to isolate the waveguide pipe. This performance is comparable to systems with corrugated waveguide or quasi-optical components. The overall excitation bandwidth of the probe is seen to be primarily determined by the final antenna or resonator used to excite the sample and its coupling to the NMR RF coil. Understanding the instrumental limitations imposed on any modulation scheme is key to understanding the observed DNP results and potentially identifying the underlying mechanisms. We demonstrate the utility of our design with a set of triangular frequency-modulated DNP experiments.

Abstract:
We study experimentally a system comprised of linear chains of spin-1/2 nuclei that provides a test-bed for multi-body dynamics and quantum information processing. This system is a paradigm for a new class of quantum information devices that can perform particular tasks even without universal control of the whole quantum system. We investigate the extent of control achievable on the system with current experimental apparatus and methods to gain information on the system state, when full tomography is not possible and in any case highly inefficient.

Abstract:
Transport of quantum information in linear spin chains has been the subject of much theoretical work. Experimental studies by nuclear spin systems in solid-state by NMR (a natural implementation of such models) is complicated since the dipolar Hamiltonian is not solely comprised of nearest-neighbor XY-Heisenberg couplings. We present here a similarity transformation between the XY-Heisenberg Hamiltonian and the grade raising Hamiltonian, an interaction which is achievable with the collective control provided by radio-frequency pulses in NMR. Not only does this second Hamiltonian allows us to simulate the information transport in a spin chain, but it also provides a means to observe its signature experimentally.

Abstract:
In a dynamic nuclear polarization experiment on a 40 mM solution of 4-amino-TEMPO in a 40:60 water/glycerol mixture, we have observed that the bulk dipolar reservoir is cooled to a spin temperature of 15.5 micro-K, following microwave irradiation for 800 s. This is significantly cooler than the 35 mK spin temperature of the Zeeman reservoir. Equilibration of the two reservoirs results in a 50 % increase in the NMR signal intensity, corresponding to a Zeeman spin temperature of 23 mK. In order to achieve this polarization directly, it was necessary to irradiate the sample with microwaves for 1500 s. Cooling of the dipolar reservoir occurs during polarization transport through the magnetic field gradient around the paramagnetic impurity, and is rapidly communicated to the bulk by dipolar spin diffusion. As dipolar spin diffusion is significantly faster than Zeeman spin diffusion, the bulk dipolar reservoir cools faster than the Zeeman reservoir. This process can be exploited to rapidly polarize the nuclear spins, by repeatedly cooling the dipolar system and transferring the polarization to the Zeeman reservoir.

Abstract:
We experimentally characterize the non-equilibrium, room-temperature magnetization dynamics of a spin chain evolving under an effective double-quantum Hamiltonian. We show that the Liouville space operators corresponding to the magnetization and the two-spin correlations evolve 90 degrees out of phase with each other, and drive the transport dynamics. For a nearest-neighbor-coupled N-spin chain, the dynamics are found to be restricted to a Liouville operator space whose dimension scales only as N^2, leading to a slow growth of multi-spin correlations. Even though long-range couplings are present in the real system, we find excellent agreement between the analytical predictions and our experimental results, confirming that leakage out of the restricted Liouville space is slow on the timescales investigated. Our results indicate that the group velocity of the magnetization is 6.04 +/- 0.38 um/s, corresponding to a coherent transport over N ~ 26 spins on the experimental timescale. As the double-quantum Hamiltonian is related to the standard one-dimensional XX Hamiltonian by a similarity transform, our results can be directly extended to XX quantum spin chains, which have been extensively studied in the context of both quantum magnetism and quantum information processing.

Abstract:
Single crystal silicon is an excellent system in which to explore dynamic nuclear polarization (DNP), as it exhibits a continuum of properties from metallic to insulating as a function of doping concentration and temperature. At low doping concentrations DNP has been observed to occur via the solid effect, while at very high doping concentrations an Overhauser mechanism is responsible. Here we report the hyperpolarization of 29Si in n-doped silicon crystals, with doping concentrations in the range of 1-3 x 10^17 /cc. In this regime exchange interactions between donors become extremely important. The sign of the enhancement in our experiments and its frequency dependence suggest that the 29Si spins are directly polarized by donor electrons via an Overhauser mechanism within exchange-coupled donor clusters. The exchange interaction between donors only needs to be larger than the silicon hyperfine interaction (typically much smaller than the donor hyperfine coupling) to enable this Overhauser mechanism. Nuclear polarization enhancement is observed for a range of donor clusters in which the exchange energy is comparable to the donor hyperfine interaction. The DNP dynamics are characterized by a single exponential time constant that depends on the microwave power, indicating that the Overhauser mechanism is the rate-limiting step. Since only about 2 % of the silicon nuclei are located within one Bohr radius of the donor electron, nuclear spin diffusion is important in transferring the polarization to all the spins. However, the spin-diffusion time is much shorter than the Overhauser time due to the relatively weak silicon hyperfine coupling strength. In a 2.35 T magnetic field at 1.1 K, we observed a DNP enhancement of $244 +/- 84 resulting in a silicon polarization of $10.4 +/- 3.4 % following two hours of microwave irradiation.

Abstract:
We have measured the decay of NMR multiple quantum coherence intensities both under the internal dipolar Hamiltonian as well as when this interaction is effectively averaged to zero, in the cubic calcium fluoride (CaF2) spin system and the pseudo one-dimensional system of fluoroapatite. In calcium fluoride the decay rates depend both on the number of correlated spins in the cluster, as well as on the coherence number. For smaller clusters, the decays depend strongly on coherence number, but this dependence weakens as the size of the cluster increases. The same scaling was observed when the coherence distribution was measured in both the usual Zeeman or z basis and the x basis. The coherence decay in the one dimensional fluoroapatite system did not change significantly as a function of the multiple quantum growth time, in contrast to the calcium fluoride case. While the growth of coherence orders is severely restricted in this case, the number of correlated spins should continue to grow, albeit more slowly. All coherence intensities were observed to decay as Gaussian functions in time. In all cases the standard deviation of the observed decay appeared to scale linearly with coherence number.

Abstract:
We show that nuclear spin subsystems can be completely controlled via microwave irradiation of resolved anisotropic hyperfine interactions with a nearby electron spin. Such indirect addressing of the nuclear spins via coupling to an electron allows us to create nuclear spin gates whose operational time is significantly faster than conventional direct addressing methods. We experimentally demonstrate the feasibility of this method on a solid-state ensemble system consisting of one electron and one nuclear spin.

Abstract:
We propose a new approach to the measurement of a single spin state, based on nuclear magnetic resonance (NMR) techniques and inspired by the coherent control over many-body systems envisaged by Quantum Information Processing (QIP). A single target spin is coupled via the natural magnetic dipolar interaction to a large ensemble of spins. Applying external radio frequency (rf) pulses, we can control the evolution of the system so that the spin ensemble reaches one of two orthogonal states whose collective properties differ depending on the state of the target spin and are easily measured. We first describe this measurement process using QIP gates; then we show how equivalent schemes can be defined in terms of the Hamiltonian of the spin system and thus implemented under conditions of real control, using well established NMR techniques. We demonstrate this method with a proof of principle experiment in ensemble liquid state NMR and simulations for small spin systems.