Broadband pulses for excitation and inversion in I = 1 systems

New composite pulses for exciting and inverting three-level systems are presented. The π/2 pulse is designed for use in quadrupole echo spectroscopy and has a bandwidth comparable to existing sequences and is slightly shorter. Two new broadband π pulses are presented which have bandwidths larger than other existing I = 1 inverting pulses without being significantly longer. Numerical calculations and experimental examples demonstrate the usefulness of the new sequences.     

Improved Broadband Inversion Performance for NMR in Liquids

New NMR broadband inversion pulses that compensate both for resonance offset and radiofrequency (RF) inhomogeneity are described. The approach described is a straightforward computer optimization of an initial digitized waveform generated from either a constant-amplitude frequency sweep or from an existing composite inversion pulse. Problems with convergence to local minima are alleviated by the way the optimization is carried out. For a given duration and maximum allowable RF field strength B₁ (but not necessarily given RMS power deposition), the resultant broadband inversion pulse (BIP) shows superior inversion compared to inversion pulses obtained from previous methods, including adiabatic inversion pulses. Any existing BIP can be systematically elaborated to build up longer inversion pulses that perform over larger and larger bandwidths. The resulting pulse need not be adiabatic throughout its duration or across the entire operational bandwidth.     

固体宽带组合脉冲的一种设计方法

用量子力学微扰方法结合相干平均理论提出了固体宽带组合脉冲的理论,并用该理论设计了固体宽带组合π脉冲P_x(90°)P_y(90°)P_x(90°),实验表明效果较好。 关键词：     

Robust slice-selective broadband refocusing pulses

Slice-selective broadband refocusing pulses are of great interest in localized MR spectroscopy for improving spatial selectivity, reducing chemical-shift displacement errors, and reducing anomalous J modulation. In practice the bandwidth of RF pulses is limited by the maximum available B1 amplitude. The goal of the present work is to design slice-selective and broadband refocusing pulses which are tolerant against B1 deviations. Pulse design is performed by numerical optimization based on optimal control theory. A comprehensive study of different cost functions and their effect on the optimization is given. The optimized slice-selective broadband refocusing pulses are compared to conventional Shinnar-Le Roux (SLR), broadband SLR, and hyperbolic secant pulses. In simulations and experiments optimized pulses were shown to fulfill broadband slice specifications over a range of ±20% B1 scalings. Experimental validation showed a reduction of chemical-shift displacement error by a factor of 3 compared to conventional SLR pulses.     

Use of composite refocusing pulses to form spin echoes

The radiofrequency pulses used in NMR are subject to a number of imperfections such as those caused by inhomogeneity of the radiofrequency (B(1)) field and an offset of the transmitter frequency from precise resonance. The effect of these pulse imperfections upon a refocusing pulse in a spin-echo experiment can be severe. Many of the worst effects, those that distort the phase of the spin echo, can be removed completely by selecting the echo coherence pathway using either the "Exorcycle" phase cycle or magnetic field gradients. It is then tempting to go further and try to improve the amplitude of the spin-echo signal by replacing the simple refocusing pulse with a broadband composite 180° pulse that compensates for the relevant pulse imperfection. We show here that all composite pulses with a symmetric or asymmetric phase shift scheme will reintroduce phase distortions into the spin echo, despite the selection of the echo coherence pathway. In contrast, all antisymmetric composite pulses yield no phase distortion whatsoever, both on and off resonance, and are therefore the correct symmetry of composite refocusing pulse to use. These conclusions are verified using simulations and (31)P MAS NMR spin-echo experiments performed on a microporous aluminophosphate.     

Exploring the limits of broadband excitation and inversion pulses

The design of broadband excitation and inversion pulses with compensation of B(1)-field inhomogeneity is a long standing goal in high resolution NMR spectroscopy. Most optimization procedures used so far have been restricted to particular pulse families to keep the scale of the problem within manageable limits. This restriction is unnecessary using efficient numerical algorithms based on optimal control theory. A systematic study of rf-limited broadband excitation by optimized pulses and broadband inversion by optimized pulses with respect to bandwidth and B(1)-field is presented. Upper limits on minimum pulse lengths are set for different degrees of pulse performance.     

Selective Decoupling

Low-power broadband decoupling sequences WALTZ-16 and GARP-1 generate large far-from-resonance frequency modulations which preclude selectivity. The framework developed to construct these broadband sequences is modified to permit selective spin decoupling. Selective-decoupling sequences are created from shaped 90° pulses combined consecutively using WALTZ permutations and supercycle symmetry while shaped 180° pulses are combined in supercycle symmetry to make inversion-based decoupling sequences. Simulations and experiments compare the decoupling bandwidth, frequency selectivity, and quality of near-resonance decoupling for broadband and selective-decoupling sequences.     

A band-selective composite gradient: application to DQF-COSY

We describe a unique band-selective method that utilizes a selective composite gradient to simultaneously achieve band selection and coherence pathway selection. This element is similar to the composite gradient known as the CLUB sandwich except the original broadband pulses have been replaced with selective pulses and the strengths of the antipolar gradients have been unbalanced. In this way, only the signals within the inversion band will continue to dephase throughout the duration of the element and satisfy the proper encoding-to-decoding gradient ratio necessary for coherence selection. Apart from the inverted polarity and asymmetry of the gradients, the band-selective CLUB sandwich is identical to the DPFGSE sequence and provides many of its desirable characteristics. We have successfully incorporated the band-selective CLUB into the DQF-COSY pulse sequence to create a band-selective experiment that offers the selectivity desired for resolution enhancement while maintaining excellent phase behavior. This is demonstrated on the congested aliphatic region of the ionophorous antibiotic Lasalocid A.     

Generation of intense sub-20-fs vacuum ultraviolet pulses compressed by material dispersion

We present our latest results on the generation of ultrashort vacuum UV (VUV) pulses by nonresonant four-wave mixing of chirped broadband pulses generated by filamentation of the fundamental of a Ti:sapphire laser with relatively narrowband pulses at the third harmonic. Positive chirp at the broadband idler yields negatively chirped VUV pulses necessary to compensate for material dispersion of a MgF(2) window in the VUV beam path. Pulse energies exceeding 400 nJ are available for time-resolved experiments. Pulse duration is measured by pump-probe ionization of Xe gas, providing the cross correlation between the fifth harmonic and the fundamental.     

Compensation of refocusing inefficiency with synchronized inversion sweep (CRISIS) in multiplicity-edited HSQC

Use of adiabatic pulses in broadband inversion and decoupling is well known. Replacement of the rectangular pi pulses in the INEPT and rev-INEPT parts of the HSQC and gHSQC experiments with adiabatic pulses substantially improves the sensitivity of these experiments. However, modulation of cross peak intensity in multiplicity-edited HSQC or gHSQC experiments can be quite severe. These modulations arise during the multiplicity-editing periods due to the inefficient refocusing of the spin-echo caused by the mismatch of the echo delay with the one-bond coupling constant. These modulations (which we call echo modulations) are field strength (and hence spectral width) independent. Use of adiabatic pulses with the inversion sweep synchronized to the 1H-13C coupling constant range typically observed in a 13C spectrum will provide substantial improvement in sensitivity. The inversion profile problems associated with rectangular pi pulses can be moderately compensated by composite pulse schemes and these schemes could prove to be reasonable alternatives to adiabatic pulses. However, the adiabatic sweep provides a unique method to compensate the echo modulations for multiplicity-edited experiments. The origin and the compensation of refocusing inefficiency with synchronized inversion sweep (CRISIS) method to minimize these modulations is described.     

Varian系统所有通道上的整形脉冲

本文介绍了Varian系统所有通道上的整形脉冲;整形脉冲的形状;波形发生器的功率适中的脉冲整形以及应用"Tophat"的选择激发;整形脉冲与选择性反转;选择性反转或宽带反转,整形脉冲的宽带激发;以及多频率激发的移层式脉冲等.     

不同宽带脉冲在钕玻璃放大器中的幅频效应

宽带脉冲在钕玻璃放大器中传输时,由于受到增益窄化和增益饱和效应的影响,脉冲频谱将受到调制,从而产生边带丢失或者频谱两侧失衡,进而导致脉冲时间波形产生调制。针对不同的宽带光源模型,数值模拟了放大器输出波形的幅度调制,分析了增益带宽、输入脉冲带宽及增益曲线中心波长相对输入脉冲中心波长的偏差等因素对输出脉冲调制度的影响。结果表明：不同的宽带光源脉冲经过钕玻璃放大器后,均会产生不同程度的幅度调制;啁啾堆积脉冲比正弦相位调制脉冲产生的幅度调制小。     

Self-referenced spectral interferometry for ultrashort infrared pulse characterization

We demonstrate for the first time (to our knowledge) characterization of ultrashort IR pulses by self-referenced spectral interferometry. Both sub-55-fs pulses from 1.4 μm to 2 μm and broadband 2.5-cycle pulses at 1.65 μm (13 fs FWHM) are characterized.     

Temporally overlapped linear frequency-chirped pulse programming for true-time-delay applications

A novel technique for programming broadband true-time delays that uses two frequency-offset temporally overlapped linear frequency-chirped pulses to produce periodic spectral gratings in an inhomogeneously broadened absorber is presented. Advantages of this technique include its ability to use chirped pulses that are longer than the coherence time of the crystal, less stringent laser frequency-stability requirements for grating accumulation, lower power requirements, a simplified system design, and the ability to tune broadband (multigigahertz) delays over a wide dynamic range (picoseconds to microseconds).     

Numerical study on the efficient generation of 351 nm broadband pulses by frequency mixing of broadband and narrowband Nd: glass lasers

Efficient frequency-tripling of phase-modulated broadband Nd:glass laser pulses is of interest to inertial confinement fusion. We report and theoretically study an efficient frequency-tripling scheme for 351 nm broadband pulses generation by use of broadband and narrowband Nd:glass lasers. Based on the conventional two-crystal doubling and tripling baseline configuration, employing an additional narrowband laser can increase the bandwidth acceptance of Nd:glass up to 320 GHz, which is 3.5 times larger than that of using the conventional configuration. The proposed scheme may also dramatically reduce the conversion of amplitude modulation from the frequency modulation. The efficiency sensitivities on both the fundamental intensity and the doubler orientation are discussed for practical applications.     

Construction of universal rotations from point-to-point transformations

For a desired range of offsets, universal rotations of arbitrary flip angle can be constructed based on point-to-point rotations of I(y) with half the flip angle. This approach allows, for example, creation of broadband or bandselective refocusing pulses from broadband or bandselective excitation pulses. Furthermore, universal rotations about any axis can be obtained from point-to-point transformations that can easily be optimized using optimal control algorithms. The construction procedure is demonstrated on the examples of a broadband refocusing pulse, a broadband 120(x) degrees rotation and a z-rotation with offset pattern.     

Phase-alternated compositeπ/2 pulses for solid state quadrupole echo NMR spectroscopy

Phase-alternated compositeπ/2 pulses have been constructed for spinI=1 to overcome quadrupole interaction effects in solid state nuclear magnetic resonance (NMR) spectroscopy. Magnus expansion approach is used to design these sequences in a manner similar to the NMR coherent averaging theory. It is inferred that the symmetric phase-alternated compositeπ/2 pulses reported here are quite successful in producing quadrupole echo free from phase distortions. This effectiveness of the present composite pulses is due to the fact that most of them are of shorter durations as compared to the ones reported in literature. In this theoretical procedure, irreducible spherical tensor operator formalism is employed to simplify the complexity involved in the evaluation of Magnus expansion terms. It has been argued in this paper that compositeπ/2 pulse sequences for this purpose can also be derived from the broadband inversionπ pulses which are designed to compensate electric field gradient (efg) inhomogeneity in spinI=1 nuclear quadrupole resonance (NQR) spectroscopy.     

Ultrashort pulse propagation in multiple-grating fiber structures

We propose a multiple-grating fiber structure that decomposes an ultrashort broadband optical pulse simultaneously in both wavelength and time. As an initial demonstration, we used a transform-limited 1-ps Gaussian pulse centered at 1.55 mu;m as the ultrashort broadband input into a three-grating fiber structure and generated three output pulses separated in wavelength and time with good correlation between experimental results and simulations. This device structure can be used to generate a multiwavelength train of pulses for use in wavelength-division-multiplexed systems or to implement frequency-domain encoding of coherent pulses for optical code-division multiple access.     

Adjustable, broadband, selective excitation with uniform phase

An advance in the problem of achieving broadband, selective, and uniform-phase excitation in NMR spectroscopy of liquids is outlined. Broadband means that, neglecting relaxation, any frequency bandwidth may be excited even when the available radiofrequency (RF) field strength is strictly limited. Selective means that sharp transition edges can be created between pure-phase excitation and no excitation at all. Uniform phase means that, neglecting spin-spin coupling, all resonance lines have nearly the same phase. Conventional uniform-phase excitation pulses (e.g., E-BURP), mostly based on amplitude modulation of the RF field, are not broadband: they have an achievable bandwidth that is strictly limited by the peak power available. Other compensated pulses based on adiabatic half-passage, like BIR-4, are not selective. By contrast, inversion pulses based on adiabatic fast passage can be broadband (and selective) in the sense above. The advance outlined is a way to reformulate these frequency modulated (FM) pulses for excitation, rather than just inversion.