Selective NMR excitation in strongly inhomogeneous magnetic fields

The NMR-MOUSE is a unilateral and mobile NMR sensor which operates with highly inhomogeneous magnetic fields. To produce a mobile NMR unit, RF excitation is sought, which can be produced with the most simple equipment, in particular nonlinear, low-power amplifiers, and to observe a free induction decay in strongly inhomogeneous fields, the excitation needs to be selective. The possibility to produce selective excitation by sequences of hard low-power radiofrequency pulses in the strongly inhomogeneous magnetic fields of the NMR-MOUSE is explored. The use of the DANTE sequence for selection of magnetization from parts of the sensitive volume was investigated for longitudinal and transverse magnetization by computer simulations and experiments. The spectra of the recorded FIDs and echo signals are in good agreement with those simulated for the excitation, which verifies the concept of the DANTE excitation. The results obtained are an important step towards a low-power operation of the NMR-MOUSE to improve its mobility.     

Selective excitation of self-assembled quantum dots by using shaped pulse

We carried out optical selective excitation of individual self-assembled quantum dots by using phase-modulated pulses. Based on scattered photoluminescence excitation resonances in individual QDs, the excitation pulses modulated in the spectral region allows for addressing individual ground states emission. The photoluminescence spectra including several QDs showed intensity changes according to both the modulation energies and phases. The results also suggested the individual control of selective QDs even in collective excitation.     

Design of a permanent magnet with a mechanical sweep suitable for variable-temperature continuous-wave and pulsed EPR spectroscopy

A magnetic system is introduced which consists of three nested rings of permanent magnets of a Halbach dipolar layout and is capable for EPR spectroscopy. Two of the rings can be rotated independently to adjust the magnetic flux in the center and even allow for mechanical field sweeps. The presented prototype achieves a magnetic flux range of 0.0282–0.3013 T with a minimal sweep of 0.15 mT and homogeneity of about 10⁻³.First applications with CW and pulsed Mims ENDOR as well as ESEEM experiments on a sample of a glycine single crystal doped with 1% copper nitrate demonstrate that flux range, sweep accuracy and homogeneity of this prototype is sufficient for EPR experiments on most solid samples.Together with a recently improved design magnets can be build which could serve as compact and easily transportable replacement of standard electromagnets with negligible consumption of power or coolants.     

Introduction to: A k-space analysis of small-tip-angle excitation

The article “A k-space analysis of small-tip-angle excitation” introduced a spatial frequency interpretation of the effect of RF excitation pulses. This introduction describes where the initial ideas for this paper came from, and traces out some of the applications that have been developed using this perspective.     

Spin-state-selective excitation in gradient-selected heteronuclear cross-polarization NMR experiments

Several heteronuclear coherence transfer mechanisms involved in proton-detected heteronuclear J-cross-polarization (HCP) NMR experiments have been theoretically derived and experimentally verified in isotropic solution. It is shown that in-phase and/or anti-phase heteronuclear coherence transfer can take place separately or simultaneously during the HCP process as a function of the relative phase between the HCP mixing sequence and the corresponding input magnetization. As the more important consequence, clean coherence-order and spin-state selective (S3) excitation with maximum sensitivity can be achieved from gradient-enhanced HCP experiments by proper co-addition/subtraction of in-phase and anti-phase magnetizations, offering an attractive alternative to widely used HSQC-type experiments.     

Abnormal electron spin echo and multiple-quantum coherence in a spin-correlated radical pair system

The phenomena of the abnormal “out-of-phase” electron spin echo in a photo-induced spin-correlated radical pair system are examined theoretically. It is shown that such abnormal phenomena are a consequence of initial non-Boltzmann distribution and zero-quantum coherence produced by laser excitation. The analysis of echo amplitude versus the pulse-angle of the microwave pulse reveals two sources for the formation of the echo. The method of excitation and detection of multiple-quantum coherence using a phase-cycled 2-pulse sequence is also discussed. Such a technique is complementary to the ESE method.     

Influence of nonlinear atomic interaction on excitation of intrinsic localized modes in carbon nanotubes

Excitation of intrinsic localized modes (ILMs) in carbon nanotubes (CNTs) with different chiral structures was investigated by molecular dynamics simulations. For CNTs with a chiral angle less than or equal to 30^°, energy concentration that continued for more than 200 fs was found in a localized area, where a pair of neighboring atoms strongly oscillated with a higher vibrational frequency than the upper bound of phonon bands. This evidently indicates excitation of the ILM. On the other hand, the ILM was not excited in CNTs with a chiral angle greater than or equal to 41^°. Analyzing the nonlinearity of the interaction between excited atoms in the ILM vibration mode, we elucidated that nonlinearity predominates the selective ILM excitation. Furthermore, stronger nonlinearity excites ILMs with both higher frequency and longer lifetime.     

On the excitation temperature of pulsed plasma produced from washer plasma gun in a compact plasma system

The washer plasma gun is widely used to produce pulsed plasma and has various applications in plasma physics. A washer plasma gun and a Guillemin-E type pulse forming network are designed and fabricated in the laboratory to produce pulsed argon plasma in the Compact Plasma System. The spectroscopic signals of pulsed plasma are taken through toughened float glass at a distance of about 0.3 m from the plasma gun by a USB4000 digital spectrometer. Assuming the gun plasma is in Local Thermodynamic Equilibrium, Boltzmann plot method and the line ratio method are used to measure the excitation/electron temperature of pulsed plasma with different base pressure varying from 0.2 mbar to 1 mbar. The excitation/electron temperature of the plasma increases slightly with increasing base pressure within the range of 0.2 mbar to 0.8 mbar and then decreases slightly at a pressure of 1 mbar. Both methods produce almost similar results in temperature measurement, but the Boltzmann Plot method is most accurate than line ratio method and widely used method to obtain the excitation/electron temperature of plasma in Local Thermodynamic equilibrium condition.     

Selective excitation of the molecular rotational wave packet by two time-delayed laser pulses

In this paper, we investigate the control of the molecular wave packet of a linear molecule by two femtosecond laser pulses. It is shown that the odd and the even rotational wave packets created by a single laser pulse can be selectively excited by accurately controlling the time delay of another laser pulse. By inserting the peak of the second laser pulse at the position of maximum or minimum value around quarter or three quarter rotational period of the slope curve with odd (or even) rotational wave packet contribution that is created by the first laser pulse, the odd rotational wave packet can be enhanced (or suppressed) while the even rotational wave packet is suppressed (or enhanced). As a result, the molecular alignments around quarter and three quarter rotational periods can be obtained. Moreover, it is also shown that by inserting the second laser pulse around the quarter or three quarter rotational periods, the changes in the maximum degree of the molecular alignment for the odd and the even rotational wave packet contributions are consistent with their corresponding slope curves at these positions.     

Anomalous pulse angle dependence of the single and double quantum echoes in a photoinduced spin-correlated coupled radical pair

In this work the response of a spin-correlated coupled radical pair to the sequence flash-t-P _ζ-τ-P _2ζ-T is investigated. For the theoretical analysis, the density operator formalism is used. Analytical expressions are derived for the electron spin single (SQ ESE) and double-quantum echoes (DQ ESE) as a function of pulse flip angle and singlet-triplet mixing angle. To illustrate the theoretical results, computer simulations are presented. In the limit of weak coupling, the “out-of-phase” SQ ESE is shown to be of a pure two-spin order having the maximal amplitude for the flip angle of 65.9°. The echo following the Hahn sequence vanishes in the same limit. This confirms the theoretical result already presented in the literature. However, the more general analysis shows that outside the weak coupling approximation the Hahn echo is of purely one-spin order, whereas the echo following the flash-t-P _ζ-τ-P _2ζ-t sequence has its maximal amplitude for the flip angle of 75° and the singlet-triplet mixing angle of 27°. The “in-phase” single- and double-quantum echoes are shown to vanish due to averaging out, within the electron spin resonance spectrometer deadtime, of contributions modulated with the sum and difference of the zero-quantum beat frequency and the frequency due to the spin-spin interaction within the pair. The calculated out-of-phase DQ ESE signal is inverted with respect to the out-of-phase SQ ESE and has only the half of its amplitude. The DQ ESE vanishes for the Hahn sequence. The echo has maximal amplitude in the weak-coupling limit for the flip angle of 65.9°. In contradiction to the analytical result previously published, the out-of-phase DQ ESE does not vanish for long τ and large zero-quantum-beat frequency.     

Electron spin polarization in an excited triplet-radical pair system: Generation and decay of the state

A computational model to simulate electron spin polarization in the three-spin-1/2 system composed of the molecular excited triplet state of (tetraphenylporphinato)zinc(II) (ZnTPP) and the doublet ground state of the 3-(N-nitronyl-notroxide) pyridine (3-NOPy) stable radical is proposed. The model is based on numerical solutions of the stochastic Liouville equation for the diffusively rotating system where the magnetic dipolar, isotropic Heisenberg exchange, and anisotropic Zeeman electron spin interactions are taken into account in a full measure, whereas the intersystem crossing processes between the singlet and triplet states of ZnTPP are considered in terms of kinetic equations for the relevant spin density matrices. Additional longitudinal and transversal paramagnetic relaxation caused by relative rotation motions of the ZnTPP and 3-NOPy moieties is taken into consideration in the form of the generalized relaxation operator.     

Comment on a shape of EPR spectra of spin-correlated radical pairs and separate radicals escaped geminate recombination

For model spin-correlated radical pairs (RPs) the EPR spectra are simulated and their shape is analyzed in detail. It is demonstrated that the widths and intensities of the EPR spectra are determined essentially by the rate of the singlet-triplet dephasing and the scale of the spin-spin interactions. It is also shown that chemical exchange of the RPs between states with different values of the exchange and the dipole-dipole interactions can produce the apparent antiphase structure lines in the EPR spectra.     

Multi-photon excitation in ZnO materials

A brief introduction on the advance in the fabrication technology of ZnO materials was given. Related research on the multi-photon excitation processes in several kinds of ZnO materials under intense pump conditions by fs pulses were reviewed. Stimulated emission properties in ZnO microtubes and nanowires have also been dealt with. Possible nonlinear effects that emerged under the extremely intense field were discussed.      

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the $\pi $ spectral phase step.     

Isotope effects in the EPR spectrum of a tin-vacancy pair in silicon

The S = 1 EPR spectrum for a tin-vacancy pair in silicon reveals easily detected isotope shifts in the fine structure splitting D for the various nuclear isotopes of tin (σD/D = + 1.0 × 10^?4 per unit mass) as well as well as those for the six near neighbor silicon atoms (σD/D = ?0.67 × 10^?4 per unit mass). These are attributed to the different vibrational amplitudes vs isotopic mass.     

In-phase selective excitation of overlapping multiplets

An editing experiment is presented that selects for a peak on the basis of its chemical shift and that of one of its scalar coupling partners. The selected multiplet is pure in-phase. The editing procedure can be used in conjunction with 1D TOCSY/HOHAHA and NOE measurements. The pulse sequence described is particularly suitable for small molecules; data is presented for Gramicidin S and dehydrotestosterone.     

Use of the Frank sequence in pulsed EPR

The Frank polyphase sequence has been applied to pulsed EPR of triarylmethyl radicals at 25 6 MHz (9.1 mT magnetic field), using 256 phase pulses. In EPR, as in NMR, use of a Frank sequence of phase steps permits pulsed FID signal acquisition with very low power microwave/RF pulses (ca. 1.5 mW in the application reported here) relative to standard pulsed EPR. A 0.2 mM aqueous solution of a triarylmethyl radical was studied using a 16 mm diameter cross-loop resonator to isolate the EPR signal detection system from the incident pulses.     

Surface excitation probabilities in surface electron spectroscopies

The phenomenon of surface excitation is competitive in nature for elastic and other inelastic scattering processes in surface electron spectroscopies; the knowledge of influence of surface excitations in electron energy loss spectra is then essential for quantitative surface analysis with these spectroscopies. The inelastic scattering of an electron moving in the vicinity of a surface is considered in a self-energy formalism to estimate the contribution of surface excitation in electron-solid interactions via the total surface excitation probability. The formulation uses the optical bulk dielectric function and provides the spatial and angular dependence of the differential and total inelastic cross-sections. The kinetic energy range of probing electrons considered is 100-5000 eV and the numerical evaluation of total surface excitation probabilities are performed for several metals, Au, Ag, Cu, Ni, Fe and Ti; empirical formulae for the surface excitation probability are given for each of these materials and compared with experimental results for the surface excitation parameter. The total surface excitation probability is higher in Ag as compared to other metals under consideration, for identical conditions of electron-solid interactions.