Thomas E. Skinner

Application of optimal control theory to the design of broadband excitation pulses for high-resolution NMR

Optimal control theory is considered as a methodology for pulse sequence design in NMR. It provides the flexibility for systematically imposing desirable constraints on spin system evolution and therefore has a wealth of applications. We have chosen an elementary example to illustrate the capabilities of the optimal control formalism: broadband, constant phase excitation which tolerates miscalibration of RF power and variations in RF homogeneity relevant for standard high-resolution probes. The chosen design criteria were transformation of I(z)-->I(x) over resonance offsets of +/- 20 kHz and RF variability of +/-5%, with a pulse length of 2 ms. Simulations of the resulting pulse transform I(z)-->0.995I(x) over the target ranges in resonance offset and RF variability. Acceptably uniform excitation is obtained over a much larger range of RF variability (approximately 45%) than the strict design limits. The pulse performs well in simulations that include homonuclear and heteronuclear J-couplings. Experimental spectra obtained from 100% 13C-labeled lysine show only minimal coupling effects, in excellent agreement with the simulations. By increasing pulse power and reducing pulse length, we demonstrate experimental excitation of 1H over +/-32 kHz, with phase variations in the spectra <8 degrees and peak amplitudes >93% of maximum. Further improvements in broadband excitation by optimized pulses (BEBOP) may be possible by applying more sophisticated implementations of the optimal control formalism.

Exploring the limits of broadband excitation and inversion: II. Rf-power optimized pulses

In [K. Kobzar, T.E. Skinner, N. Khaneja, S.J. Glaser, B. Luy, Exploring the limits of broadband excitation and inversion, J. Magn. Reson. 170 (2004) 236-243], optimal control theory was employed in a systematic study to establish physical limits for the minimum rf-amplitudes required in broadband excitation and inversion pulses. In a number of cases, however, experimental schemes are not limited by rf-amplitudes, but by the overall rf-power applied to a sample. We therefore conducted a second systematic study of excitation and inversion pulses of varying pulse durations with respect to bandwidth and rf-tolerances, but this time using a modified algorithm involving restricted rf-power. The resulting pulses display a variety of pulse shapes with highly modulated rf-amplitudes and generally show better performance than corresponding pulses with identical pulse length and rf-power, but limited rf-amplitude. A detailed description of pulse shapes and their performance is given for the so-called power-BEBOP and power-BIBOP pulses.

Shaped optimal control pulses for increased excitation bandwidth in EPR

A 1 ns resolution pulse shaping unit has been developed for pulsed EPR spectroscopy to enable 14-bit amplitude and phase modulation. Shaped broadband excitation pulses designed using optimal control theory (OCT) have been tested with this device at X-band frequency (9 GHz). FT-EPR experiments on organic radicals in solution have been performed with the new pulses, designed for uniform excitation over a significantly increased bandwidth compared to a classical rectangular π/2 pulse of the same B(1) amplitude. The concept of a dead-time compensated prefocused pulse has been introduced to EPR with a self-refocusing of 200 ns after the end of the pulse. Echo-like refocused signals have been recorded and compared to the performance of a classical Hahn-echo sequence. The impulse response function of the microwave setup has been measured and incorporated into the algorithm for designing OCT pulses, resulting in further significant improvements in performance. Experimental limitations and potential new applications of OCT pulses in EPR spectroscopy will be discussed.

Exploring the limits of broadband 90° and 180° universal rotation pulses.

90° and 180° universal rotation (UR) pulses are two of the most important classes of pulses in modern NMR spectroscopy. This article presents a systematic study characterizing the achievable performance of these pulses as functions of bandwidth, pulse length, and tolerance to B(1)-field inhomogeneity/miscalibration. After an evaluation of different quality factors employed in pulse design algorithms based on optimal control theory, resulting pulses are discussed in detail with a special focus on pulse symmetry. The vast majority of resulting BURBOP (broadband universal rotations by optimal control) pulses are either fully symmetric or have one symmetric and one antisymmetric Cartesian rf component, where the importance of the first symmetry has not been demonstrated yet and the latter one matches the symmetry that results from a previously derived construction principle of universal rotation pulses out of point-to-point pulses [3]. Optimized BURBOP pulses are shown to perform better than previously reported UR pulses, resulting in shorter pulse durations for the same quality of broadband rotations. From a comparison of qualities of effective universal rotations, we find that the application of a single optimal refocusing pulse matches or improves the performance of two consecutive inversion pulses in INEPT-like pulse sequence elements of the same total duration.

Universal scaling of the formation factor in porous media derived by combining percolation and effective medium theories

The porosity dependence of the formation factor for geologic media is examined from the perspective of universal scaling laws from percolation and effective medium theories. Over much of the range of observed porosity, the expected percolation scaling is observed, but the values of the numerical prefactor do not conform to the simple predictions from percolation theory. Combining effective medium and percolation theories produces a numerical prefactor whose value depends on both the threshold porosity and the porosity above which the formation factor crosses from percolation to effective medium scaling. This change allows extraction of a numerical value of the prefactor, which is reasonably close to experimental values. Subsequent evaluation of the porosity dependence of the formation factor shows that difficulties in prior comparisons of theory and experiment are largely removed when percolation scaling is allowed to transition to effective medium scaling far above the percolation threshold.

Detection of neutral oxygen and sulfur emissions near Io using IUE

IUE spectra have shown several O I and S I emissions near Io. The optical thickness of the S I 1814 A multiplet indicates that the S column density is greater than about 2 x 10 to the 12th/sq cm. The presence of an S I 1479 A feature suggests that electron collisions with SO2 could be a major source of the emissions. It is likely that particle excitation in the denser collision-dominated part of the atmosphere is also responsible for a substantial part of the observed emissions.

Linear Phase Slope in Pulse Design: Application to Coherence Transfer

Using optimal control methods, robust broadband excitation pulses can be designed with a defined linear phase dispersion. Applications include increased bandwidth for a given pulse length compared to equivalent pulses requiring no phase correction, selective pulses, and pulses that mitigate the effects of relaxation. This also makes it possible to create pulses that are equivalent to ideal hard pulses followed by an effective evolution period. For example, in applications, where the excitation pulse is followed by a constant delay, e.g. for the evolution of heteronuclear couplings, part of the pulse duration can be absorbed in existing delays, significantly reducing the time overhead of long, highly robust pulses. We refer to the class of such excitation pulses with a defined linear phase dispersion as ICEBERG pulses (Inherent Coherence Evolution optimized Broadband Excitation Resulting in constant phase Gradients). A systematic study of the dependence of the excitation efficiency on the phase dispersion of the excitation pulses is presented, which reveals surprising opportunities for improved pulse sequence performance.

Long-term stability of the Io high-temperature plasma torus

The short wavelength camera of the International Ultraviolet Explorer satellite was used to measure S II 1256, S III 1199, semiforbidden S III 1729, and semiforbidden S IV 1406 emission from the high-temperature region of the Io plasma torus. Observations over a period of five years (1979-1984) indicate that the Io plasma parameters have relatively small variations, particularly in the case of the mixing ratio for the dominant constituent S(++), and electron temperature. A simple three-dimensional model of the plasma torus was used to obtain the ion mixing ratios and the plasma density for each observation. The results are compared with Voyager 1 data for mixing ratio (ion density divided by electron density); ionization balance; and plasma density. The results of the comparison are discussed in detail.

IUE observations of longitudinal and temporal variations in the Jovian auroral emission

The IUEs short wavelength spectrograph has been used to monitor the auroral emissions from Jupiters northern hemisphere, yielding eight observations between January 1981 and January 1982 of H I Lyman-alpha and the H2 Lyman and Werner bands. Attention is given to an apparent periodic emission flux fluctuation, through detailed modeling of the emission geometry. Two possible auroral zones are defined at the north pole by mapping the magnetic field lines from the Io torus and the magnetotail onto the planets atmosphere. The observed variation in flux with central meridian longitude is not consistent with a uniform brightness as a function of magnetic longitude in either auroral zone. The data can be fitted by confining the emissions to the region of the northern torus auroral zone, in qualitative agreement with the magnetic anomaly model. A similar emission from the magnetotail auroral zone cannot be ruled out.

Saturation-Dependence of Dispersion in Porous Media

In this study, we develop a saturation-dependent treatment of dispersion in porous media using concepts from critical path analysis, cluster statistics of percolation, and fractal scaling of percolation clusters. We calculate spatial solute distributions as a function of time and calculate arrival time distributions as a function of system size. Our previous results correctly predict the range of observed dispersivity values over ten orders of magnitude in experimental length scale, but that theory contains no explicit dependence on porosity or relative saturation. This omission complicates comparisons with experimental results for dispersion, which are often conducted at saturation less than 1. We now make specific comparisons of our predictions for the arrival time distribution with experiments on a single column over a range of saturations. This comparison suggests that the most important predictor of such distributions as a function of saturation is not the value of the saturation per se, but the applicability of either random or invasion percolation models, depending on experimental conditions.