A Vector Model of Adiabatic Decoupling

A vector model of adiabatic decoupling is enunciated for an IS-coupled system of two spin- heteronuclei in the high-power limit of ideal adiabatic pulses. The observed S-spin magnetization evolves according to a time-dependent coupling that scales as thezcomponent of an I-spin vector which evolves due to the applied decoupling irradiation. Simple analytical expressions are derived both on and off resonance for the reduced coupling during an ideal sech/tanh inversion pulse and for the resulting signal when either in-phase or antiphase magnetization is present at the start of decoupling. The resulting model allows one to readily envision decoupling experiments, make accurate estimates of sideband intensity, and assess the relative performance of different decoupling schemes. The utility of the model is further demonstrated by applying it to several recently proposed methods for reducing sidebands. In the limit of ideal adiabatic pulses, the predictions of the vector model are almost identical to those of quantum mechanics. At the lower RF power levels used in practical adiabatic decoupling applications, where the pulses are no longer perfectly adiabatic, phase cycles are employed to achieve performance that approximates the ideal limits derived here, so the vector model is more generally applicable, as well. These limits establish standards for future determination of the most efficient parameters for practical applications of broadband adiabatic decoupling in a single transient.     

Synchronized adiabatic decoupling

A new decoupling scheme termed "synchronized adiabatic decoupling" is developed for use in the indirectly detected dimension. After each increment, the decoupling sequence is replaced by another one with different period T or different initial period T(ini) so that sampling always occurs at the end of a complete decoupling period. The effects of J coupling are therefore completely averaged out for all data points. As a result, all decoupling sidebands disappear and the center band increases correspondingly. Since the synchronized adiabatic decoupling does not require conventional editing techniques to cancel the sidebands, it is useful in high-field gradient-enhanced multidimensional experiments with only a single scan per increment.     

Calibration of STUD+ Parameters to Achieve Optimally Efficient Broadband Adiabatic Decoupling in a Single Transient

To provide the most efficient conditions for spin decoupling with least RF power, master calibration curves are provided for the maximum centerband amplitude, and the minimum amplitude for the largest cycling sideband, resulting from STUD+ adiabatic decoupling applied during a single free induction decay. The principal curve is defined as a function of the four most critical experimental input parameters: the maximum amplitude of the RF field,RF_max, the length of the sech/tanh pulse,T_p, the extent of the frequency sweep,bwdth,and the coupling constant,J_o. Less critical parameters, the effective (or actual) decoupled bandwidth,bw_eff, and the sech/tanh truncation factor, β, which become more important asbwdthis decreased, are calibrated in separate curves. The relative importance of nine additional factors in determining optimal decoupling performance in a single transient are considered. Specific parameters for efficient adiabatic decoupling can be determined via a set of four equations which will be most useful for¹³C decoupling, covering the range of one-bond¹³C¹H coupling constants from 125 to 225 Hz, and decoupled bandwidths of 7 to 100 kHz, with a bandwidth of 100 kHz being the requirement for a 2 GHz spectrometer. The four equations are derived from a recent vector model of adiabatic decoupling, and experiment, supported by computer simulations. The vector model predicts an inverse linear relation between the centerband and maximum sideband amplitudes, and it predicts a simple parabolic relationship between maximum sideband amplitude and the productJ_oT_p. The ratiobwdth/(RF_max)²can be viewed as a characteristic time scale, τ_c, affecting sideband levels, with τ_c≈T_pgiving the most efficient STUD+ decoupling, as suggested by the adiabatic condition. Functional relationships betweenbwdthand less critical parameters,bw_effand β, for efficient decoupling can be derived from Bloch-equation calculations of the inversion profile for a single sech/tanh pulse. Residual splitting of the centerband, normally associated with incomplete or inefficient decoupling, is not seen in sech/tanh decoupling and therefore cannot be used as a measure of adiabatic decoupling efficiency. The calibrated experimental performance levels achieved in this study are within 20% of theoretical performance levels derived previously for ideal sech/tanh decoupling at high power, indicating a small scope for further improvement at practical RF power levels. The optimization procedures employed here will be generally applicable to any good combination of adiabatic inversion pulse and phase cycle.     

Excited-configuration metastable level lifetimes of Cl-like Mn IX and Fe X

Forbidden transitions from levels with 3P and 1D cores in excited configurations of Cl-like Mn IX and Fe X have been isolated using interference filters. The fluorescence decay lifetimes of ions orbiting in a Kingdon ion trap were measured. New relativistic configuration interaction calculations of relevant level lifetimes, to aid the analysis, based on B-spline basis sets, are also presented. Line identifications and experimental lifetimes are Mn IX ((4)D(7/2)-(4)F(9/2)):363(-3/+7) nm; tau(Mn IX3p(4)(3P)3d (4)F(9/2)) = 210+/-42 ms; tau(Fe X,3p(4)(3P)3d (4)F(9/2)) = 85.7+/-9.2 ms; tau(Fe X,3p(4)(3P)3d (4)F(7/2)) = 93+/-30 ms; and tau(Fe X, 3p(4)(1D)3d (2)G(9/2)) = 17.8+/-3.1 ms.     

A new decoupling method for accurate quantification of polyethylene copolymer composition and triad sequence distribution with 13C NMR

(13)C NMR is a powerful analytical tool for characterizing polyethylene copolymer composition and sequence distribution. Accurate characterization of the composition and sequence distribution is critical for researchers in industry and academia. Some common composite pulse decoupling (CPD) sequences used in polyethylene copolymer (13)C NMR can lead to artifacts such as modulations of the decoupled (13)C NMR signals (decoupling sidebands) resulting in systematic errors in quantitative analysis. A new CPD method was developed, which suppresses decoupling sidebands below the limit of detection (less than 1:40,000 compared to the intensity of the decoupled signal). This new CPD sequence consists of an improved Waltz-16 CPD, implemented as a bilevel method. Compared with other conventional CPD programs this new decoupling method produced the cleanest (13)C NMR spectra for polyethylene copolymer composition and triad sequence distribution analyses.     

Measurement of the lifetime difference in the B0(s) system

We present a study of the decay B0(s) --> J/psiphi. We obtain the CP-odd fraction in the final state at time zero, Rperpendicular = 0.16 +/- 0.10(stat) +/- 0.02 (syst), the average lifetime of the (B0(s), B0(s)) system, tau(B0(s)) = 1.39(+0.13)(-0.16)(stat)(+0.01)(-0.02)(syst) ps, and the relative width difference between the heavy and light mass eigenstates, DeltaGamma/Gamma tripple bond (GammaL - GammaH)/Gamma = 0.24(+0.28)(-0.38)(stat)(+0.03)(-0.04)(syst). With the additional constraint from the world average of the lifetime measurements using semileptonic decays, we find tau(B0(s)) = 1.39 +/- 0.06 ps and DeltaGamma/Gamma = 0.25(+0.14)(-0.15). For the ratio of the B0(s) and B0 lifetimes we obtain tau(B0(s))/tau(B0) = 0.91 +/- 0.09(stat) +/- 0.003(syst).     

Observation of B(0) --> D0pi(0) and B(0) -->D(*0)pi(0)

We have studied the color-suppressed hadronic decays of neutral B mesons into the final states D*0pi(0). Using 9.67 x 10(6) BB pairs collected with the CLEO detector, we observe the decays B( 0) --> D0pi(0) and B( 0) -->D(*0)pi(0) with the branching fractions BB( 0) -->D0pi(0)) = (2.74(+0.36)(-0.32) +/- 0.55)x10(-4) and BB( 0) -->D(*0)pi(0)) = (2.20(+0.59)(-0.52) +/- 0.79)x10(-4). The first error is statistical and the second systematic. The statistical significance of the D0pi(0) signal is 12.1sigma ( 5.9sigma for D(*0)pi(0)). Utilizing the B( 0) -->D*0)pi(0) branching fractions we determine the strong phases delta(I,D(*)) between isospin 1/2 and 3/2 amplitudes in the Dpi and D*pi final states to be cosdelta(I,D) = 0.89 +/-0.08 and cosdelta(I,D*) = 0.89 +/- 0.08, respectively.     

Measurement of the lifetime difference between Bs mass eigenstates

We present measurements of the lifetimes and polarization amplitudes for B(0)(s)-->J/psiphi and B(0)(d)-->J/psiK(*0) decays. Lifetimes of the heavy and light mass eigenstates in the B(0)(s) system are separately measured for the first time by determining the relative contributions of amplitudes with definite CP as a function of the decay time. Using 203+/-15 B(0)(s) decays we obtain tau(L) = (1.05(+0.16)(-0.13) +/- 0.02) ps and tau(H) = (2.07(+0.58)(-0.46) +/- 0.03) ps. Expressed in terms of the difference DeltaGamma(s) and average Gamma(s), of the decay rates of the two eigenstates, the results are DeltaGamma(s)/Gamma(s) = (65(+25)(-33) +/- 1)% and DeltaGamma(s) = (0.47(+0.19)(-0.24) +/- 0.01) ps(-1).     

Effects of a parallel magnetic field on the metal-insulator transition in a dilute two-dimensional electron system

The temperature dependence of conductivity sigma(T) of a two-dimensional electron system in silicon has been studied in parallel magnetic fields B. At B = 0, the system displays a metal-insulator transition at a critical electron density n(c)(0), and dsigma/dT>0 in the metallic phase. At low fields ( B < or approximately equal to 2 T), n(c) increases as n(c)(B)-n(c)(0) proportional, variant Bbeta ( beta approximately 1), and the zero-temperature conductivity scales as sigma(n(s),B,T = 0)/sigma(n(s),0,0) = f(B(beta)/delta(n)), where delta(n) = [n(s)-n(c)(0)]/n(c)(0) and n(s) is electron density, as expected for a quantum phase transition. The metallic phase persists in fields of up to 18 T, consistent with the saturation of n(c) at high fields.     

Dephasing relaxation of the electron spin echo of the vibronic Cu(H(2)O)(6) complexes in Tutton salt crystals at low temperatures.

Two-pulse electron spin echo (ESE) measurements of the phase relaxation (phase memory time T(M)) were performed in a series of Tutton salt crystals M(I)(2)M(II)(SO(4))(2).6X(2)O (M(I)=NH(4), K, Cs; M(II)=Zn, Mg; X=H, D) weakly doped with Cu(2+) ions (c approximately equal to 10(18) ions/cm(3)) in temperature range 4-60 K where ESE signals were detectable. The ESE decay was strongly modulated with proton (or deuteron) frequencies and described by the decay function V(2tau)=V(0)exp(-btau-mtau(2)) with the mtau(2) term being temperature independent and negligible above 20 K. Various mechanisms leading to the tau- or tau(2)-type ESE decay are reviewed. The m and b coefficients for nuclear spectral diffusion (NSD), electron spectral diffusion (SD), and instantaneous diffusion (ID) were calculated in terms of existing theories and the resulting rigid lattice T(0)(M) times were found to be close one to another within the crystal family with average values: 17.5 micros (NSD protons), 200 micros (NSD deuterons), 8 micros (SD), and 5 micros (ID). The ID dominates but the calculated effective T(M)(0) is longer than the experimental T(M)(0)=2 micros. This is due to a nonuniform distribution of the Cu(2+) ions with a various degree of the disorder in the studied crystals. The acceleration of the dephasing rate 1/T(M) with temperature is due to the mechanisms producing exp(-btau) decay. They are reviewed and two of them were found to be operative in Tutton salt crystals: (a) Excitations to the vibronic levels of energy Delta leading to the temperature dependence 1/T(M)=B exp(-Delta/kT), with the vibronic levels produced by strong Jahn-Teller effect, and (b) spin-lattice relaxation processes being effective above 50 K. Based on the Delta values being on the order of 100 cm(-1), the scheme of vibronic levels in the Tutton salts is presented, and the independence of the Delta on temperature proves that the adiabatic potential surface shape of Jahn-Teller active Cu(H(2)O)(6) complexes is not affected by temperature below 65 K.     

Search for quadrupole strength in the electroexcitation of the delta+(1232)

High-precision 1H(e,e'p)pi(0) measurements at Q2 = 0.126 (GeV/c)2 are reported, which allow the determination of quadrupole amplitudes in the gamma*N-->Delta transition; they simultaneously test the reliability of electroproduction models. The derived quadrupole-to-dipole ( I = 3/2) amplitude ratios, R(SM) = (-6.5+/-0.2(stat+sys)+/-2.5(mod))% and R(EM) = (-2.1+/-0.2(stat+sys)+/-2.0(mod))%, are dominated by model error. Previous R(SM) and R(EM) results should be reconsidered after the model uncertainties associated with the method of their extraction are taken into account.     

"BEST" homonuclear adiabatic decoupling for 13C- and 15N-double-labeled proteins.

The cyclic irradiation sidebands appearing in homonuclear adiabatic decoupling are calculated in detail, which reveals the origin of the antisymmetric sidebands. The sidebands can be inverted by inserting an initial decoupling with a different period, but the same f1rms as the main decoupling that is required for Bloch-Siegert shift compensation. The sidebands can be eliminated in a broad decoupling range by adding spectra of opposite sidebands. Based on this scheme, an offset-independent double-adiabatic decoupling, named Bloch-Siegert Shift Eliminated and Cyclic Sideband Trimmed Double-Adiabatic Decoupling, or "BEST" decoupling for short, is constructed, which not only compensates the Bloch-Siegert shift as shown earlier by Zhang and Gorenstein (1998) but also eliminates residual sidebands effectively.     

Decoupling Bang-Bang Group for Adiabatic Decoherence Control in a Three-Level Atom

In this paper, we study the control problem of adiabatic decoherence in a three-level atom. We will find the decoupling bang-bang group for various configurations, including the V configuration and the cascade type of three-levelatom subjected to adiabatic decoherence. We also give the programs to design a sequence of periodic twinborn pulses to suppress the decoherence.     

“BEST” Homonuclear Adiabatic Decoupling for C- and N-Double-Labeled Proteins

The cyclic irradiation sidebands appearing in homonuclear adiabatic decoupling are calculated in detail, which reveals the origin of the antisymmetric sidebands. The sidebands can be inverted by inserting an initial decoupling with a different period, but the same f_1rms as the main decoupling that is required for Bloch–Siegert shift compensation. The sidebands can be eliminated in a broad decoupling range by adding spectra of opposite sidebands. Based on this scheme, an offset-independent double-adiabatic decoupling, named Bloch–Siegert Shift Eliminated and Cyclic Sideband Trimmed Double-Adiabatic Decoupling, or “BEST” decoupling for short, is constructed, which not only compensates the Bloch–Siegert shift as shown earlier by Zhang and Gorenstein (1998) but also eliminates residual sidebands effectively.     

Measurement of the Lambda0b lifetime in the decay lambda0b--> J/psiLambda0 with the D0 detector

We present measurements of the Lambda(0)(b) lifetime in the exclusive decay channel Lambda(0)(b)--> J/psiLambda(0), with J/psi--> mu(+)mu(-) and Lambda(0)--> ppi(-), the B0 lifetime in the decay B0-->J/psiK(0)(S) with J/psi--> mu(+)mu(-) and K(0)(S)-->pi(+)pi(-), and the ratio of these lifetimes. The analysis is based on approximately 250 pb(-1) of data recorded with the D0 detector in pp collisions at sqrt[s] = 1.96 TeV. The Lambda(0)(b) lifetime is determined to be tau(Lambda(0)(b)) = 1.22(+0.22)(-0.18)(stat) +/- 0.04(syst) ps, the B0 lifetime tau(B0) = 1.40(+0.11)(-0.10)(stat) +/- 0.03(syst) ps, and the ratio tau(Lambda(0)(b))/tau(B0) = 0.87(+0.17)(-0.14)(stat) +/- 0.03(syst). In contrast with previous measurements using semileptonic decays, this is the first determination of the Lambda(0)(b) lifetime based on a fully reconstructed decay channel.     

Measurement of the decay amplitudes of B0 --> J/psiK*0 and B(s)(0) --> J/psistraight phi decays

An angular analysis of B0-->J/psiK(*0) and B(0)(s)-->J/psistraight phi has been used to determine the decay amplitudes with parity-even longitudinal ( A0) and transverse ( A( parallel)) polarization and parity-odd transverse ( A( perpendicular)) polarization. The measurements are based on 190 B0 and 40 B(0)(s) candidates obtained from 89 pb(-1) of &pmacr;p collisions at the Fermilab Tevatron. The longitudinal decay amplitude dominates with |A0|(2) = 0.59+/-0. 06+/-0.01 for B0 and |A0|(2) = 0.61+/-0.14+/-0.02 for B(0)(s) decays. The parity-odd amplitude is found to be small with |A( perpendicular)|(2) = 0.13(+0.12)(-0.09)+/-0.06 for B0 and |A( perpendicular)|(2) = 0.23+/-0.19+/-0.04 for B(0)(s) decays.     

电流磁场作用下YBCO颗粒膜的非平衡微波响应

文中从二维 Josephson弱连接网络模型出发 ,讨论了二维超导体系的磁通“涡流 -反涡流”束缚对的激发问题 ,并进一步讨论了涡旋在电流、磁场作用下的激发问题 ,给出了自由涡旋的密度分布 n(I,H ,T)随温度的分布图 ,对比高温超导体的非平稳微波响应曲线图 ,发现两者具有相似的分布特征。该结果表明 ,高温超导体的非平稳微波响应与磁通“涡旋 -反涡旋”束缚对的激发有关。     

Test of a method for sampling the internal degrees of freedom of a flexible solute molecule based on adiabatic decoupling and temperature or force scaling

Simulation of the folding equilibrium of a polypeptide in solution is a computational challenge. Standard molecular dynamics (MD) simulations of such systems cover hundreds of nanoseconds, which is barely sufficient to obtain converged ensemble averages for properties that depend both on folded and unfolded peptide conformations. If one is not interested in dynamical properties of the solute, techniques to enhance the conformational sampling can be used to obtain the equilibrium properties more efficiently. Here the effect on particular equilibrium properties at 298?K of adiabatically decoupling the motion a β-hepta-peptide from the motion of the solvent and subsequently up-scaling its temperature or down-scaling the forces acting on it is investigated. The ensemble averages and rate of convergence are compared to those for standard MD simulations at two different temperatures and a simulation in which the temperature of the solute is increased to 340?K while keeping the solvent at 298?K. Adiabatic decoupling with a solute mass scaling factor s _m ?=?100 and a temperature scaling factor of s _T ?=?1.1 seems to slightly increase the convergence of several properties such as enthalpy of folding, NMR NOE atom–atom distances and ³J-couplings compared to a standard MD simulation at 298?K. Convergence is still slower than that observed at 340?K. The system with a temperature of 340?K for the solute and 298?K for the solvent without scaling of the mass converges fastest. Using a force scaling factor s _V ?=?0.909 perturbs the system too much and leads to a destabilization of the folded structure. The sampling efficiency and possible distortive effects on the configurational distribution of the solute degrees of freedom due to adiabatic decoupling and temperature or force scaling are also analysed for a simpler model, a dichloroethane molecule in water. It appears that an up-scaling of the mass of the solute reduces the sampling more than the subsequent up-scaling of the temperature or down-scaling of the force enhances it. This means that adiabatic decoupling the solute degrees of freedom from the solvent ones followed by an up-scaling of temperature of down-scaling of the forces does not lead to significantly enhanced sampling of the folding equilibrium.     

Rotor-synchronized acquisition of quadrupolar satellite-transition NMR spectra: practical aspects and double-quantum filtration

The very broad resonances of quadrupolar (spin I > 1/2) nuclei are resolved by magic angle spinning (MAS) into a large number of spinning sidebands, each of which often remains anisotropically broadened. The quadrupolar interaction can be removed to a first-order approximation if the MAS NMR spectrum is acquired in a rotor-synchronized fashion, aliasing the spinning sidebands onto a centreband and thereby increasing the signal-to-noise ratio in the resulting, possibly second-order broadened, spectrum. We discuss the practical aspects of this rotor-synchronization in the direct (t(2)) time domain, demonstrating that the audiofrequency filters in the receiver section of the spectrometer have a significant impact on the precise timings needed in the experiment. We also introduce a novel double-quantum filtered rotor-synchronized experiment for half-integer spin quadrupolar (spin I = 3/2, 5/2, etc.) nuclei that makes use of central-transition-selective inversion pulses to both excite and reconvert double-quantum coherences and yields a simplified spectrum containing only the ST(1) (m(I) = +/-1/2 <--> +/-3/2) satellite-transition lineshapes. For spin I = 5/2 nuclei, such as (17)O and (27)Al, this spectrum may exhibit a significant resolution increase over the conventional central-transition spectrum.     

The proton inventory technique in a dual mechanistic system: the spontaneous hydrolysis of ethyl formate

Ethyl formate undergoes spontaneous hydrolysis through two parallel mechanistic pathways: water catalysis and specific hydrogen-ion catalysis. The proton inventory of the water reaction at 37.0 ( degrees )C was determined from the overall conversion curves, in H(2)O/D(2)O mixtures of deuterium atom fraction n, resulting in k(1)(n)=(2.1+/-0.1)x10(-5) s(-1) (1-n+0.42 n) (1-n+0.83 n)(2), in agreement with the results of six other cases of carboxylic acid derivatives. This result contributes to the validation of the accuracy of the proton inventory technique.