S. Warren

Coherent Control of Quantum Dynamics: The Dream Is Alive

Current experimental and theoretical progress toward the goal of controlling quantum dynamics is summarized. Two key developments have now revitalized the field. First, appropriate ultrafast laser pulse shaping capabilities have only recently become practical. Second, the introduction of engineering control concepts has put the required theoretical framework on a rigorous foundation. Extrapolations to determine what is realistically possible are presented.

Femtosecond laser pulse shaping by use of microsecond radio-frequency pulses

We demonstrate a new pulse-shaping technique, using an acousto-optic modulator as a spatial modulator in a zero-dispersion delay line. Compared with existing techniques, this approach simplifies optical alignment and dramatically improves update rates. It should also improve flexibility for generating complex waveforms.

Quantum treatment of the effects of dipole–dipole interactions in liquid nuclear magnetic resonance

Experimental observation of anomalous intermolecular cross‐peaks in two‐dimensional solution NMR spectra have attracted significant recent attention. Extremely simple pulse sequences on extremely simple samples with large equilibrium magnetization give resonances in the indirectly detected dimension which are simply impossible in the conventional density matrix framework of NMR. Here we extend a recently proposed density matrix treatment [Science 262, 2005 (1993)] to calculate the exact time evolution for a variety of pulse sequences. This density matrix treatment explicitly removes two fundamental assumptions of the standard theory—it includes the dipolar interaction between spins in solution (which is only partially averaged away by diffusion) and completely removes the high temperature approximation to the equilibrium density matrix [exp(−βH)≊1−βH]. We compare this quantum mechanical treatment to a corrected classical model, which modifies the dipolar demagnetizing field formulation to account for the ...

Homogeneous NMR Spectra in Inhomogeneous Fields

Researchers interested in high-resolution nuclear magnetic resonance (NMR) spectroscopy have long sought higher magnetic fields to enhance resolution and simplify spectra. Magnets with substantially larger fields than those available in the best commercial spectrometers are available, but the inhomogeneity is unacceptable for high-resolution spectra. A detection method (termed HOMOGENIZED) is presented that removes inhomogeneity while retaining chemical shift differences and J couplings. With existing inhomogeneous magnets, this method could nearly double the largest resonance frequency available for high-resolution NMR. The HOMOGENIZED sequence is based on observations of intermolecular zero-quantum coherences between a solute molecule and solvent molecules that are micrometers away; as long as the field is homogeneous over this short distance, sharp resonances are recovered without echoes. Experimental demonstrations and a detailed density matrix theory to explain the effect are presented.

Theory of selective excitation of multiple‐quantum transitions

The question of whether a molecule can be made to absorb and emit photons only in groups of n is treated. Pulse sequences are introduced which in effect selectively induce the absorption of only groups of n photons. This causes only n-quantum transitions even when many other transitions might be resonant. The technique involves repeated phase shifts of 2pi/n in the radiation to build up the selected coherences and cancel all other coherences, and is applicable to a wide range of spectroscopic systems. Coherent averaging theory is extended to describe selective sequences and demonstrates that n-quantum selectivity is possible to arbitrarily high order in the average Hamiltonian expansion. High-order selectivity requires many phase shifts, however, and for this reason the residual nonselective effects of sequences which are selective to only a finite order are calculated. Selective sequences are applied to the multiple-quantum NMR of oriented molecules, where in combination with time reversal sequences they produce a much more efficient transfer of the population differences into selected coherences than is obtainable by normal wideband pumping. For example, the 10-quantum transition in a 10-spin system can be enhanced by more than four orders of magnitude. Experiments on selective excitaiton of the 4-quantum transitions in oriented benzene verify the expected enhancement.

Increasing hyperpolarized spin lifetimes through true singlet eigenstates.

The sensitivity limitations for magnetic resonance imaging of organic molecules have recently been addressed by hyperpolarization methods, which prepare excess nuclear spin polarization. This approach can increase sensitivity by orders of magnitude, but the enhanced signal relaxes away in tens of seconds, even in favorable cases. Here we show theoretically that singlet states between strongly coupled spins in molecules can be used to store and retrieve population in very-long-lived disconnected eigenstates, as long as the coupling between the spins substantially exceeds both the couplings to other spins and the resonance frequency difference between them. Experimentally, 2,3-carbon-13–labeled diacetyl has a disconnected eigenstate that can store population for minutes and is read out by hydration to make the two spins inequivalent.

Imaging with intermolecular multiple-quantum coherences in solution nuclear magnetic resonance

A magnetic resonance imaging technique based on intermolecular multiple-quantum coherences in solution (the correlated spectroscopy revamped by asymmetric z gradient echo detection or CRAZED experiment) is described here. Correlations between spins in different molecules were detected by magnetic-field gradient pulses. In order for a correlation to yield an observable signal, the separation between the two spins must be within a narrow band that depends on the area of the gradient pulses. The separation can be tuned from less than 10 micrometers to more than 1 millimeter, a convenient range for many applications.

Effects of arbitrary laser or NMR pulse shapes on population inversion and coherence

We present a new perturbation expansion for calculating the effects of arbitrary pulse shapes in two‐level systems, even when the effects are grossly nonlinear. The first two terms have simple physical interpretations. This expansion converges rapidly for all values of resonance offset with simple shapes, and for any pulse shape far from resonance. We generate very simple, symmetric, single phase pulse shapes which produce uniform inversion or polarization and which can be combined into multiple pulse sequences. We also show that pulse shape modification is superior to construction of composite pulse sequences, since such sequences must become erratic far from resonance.

Intermolecular multiple-quantum coherences and cross correlations in solution nuclear magnetic resonance

It was recently reported that multiple‐quantum NMR coherences could apparently be observed in water and other concentrated samples, in direct violation of established theory. These results were previously explained in a dressed‐state framework as manifestations of the coupling between the spins and the coil (quantized radiation damping). Here we provide details of previously communicated experimental explorations of these effects [J. Chem. Phys. 96, 1659 (1992)], and we extend these results to multicomponent samples. We observe cross peaks between independent molecules in solution in two‐dimensional experiments, including spectra with multiple‐quantum coherence transfer echoes; we also demonstrate coherence transfer between solvent and (dilute) solute molecules. However, we show that these intermolecular cross peaks are induced by a mechanism which is local in nature, and thus radiation damping (either classical or quantized) cannot provide the bulk of the explanation for their occurrence. Simulations and...

Ultrafast pulse shaping: amplification and characterization

We demonstrate high-resolution amplified pulse shaping using an acousto-optic modulator (AOM) at a center-wavelength of 795nm. The output pulses have energy of 200mJ/pulse and a transform-limited pulsewidth of 150fs. A spectral modulation of over 40 features is achieved in a single pulse. We characterize the pulses using the STRUT (Spectrally and Temporally Resolved Upconversion Technique). Using predistortion techniques, we demonstrate that the pulses can be shaped in amplitude and phase. We create a complex pulse shape with hyperbolic secant amplitude and hyperbolic tangent frequency sweep, which is useful for applications in adiabatic rapid passage experiments.