Excitation Bandwidth Research Articles

Understanding the Linewidth of the ESR Spectrum Detected by a Single NV Center in Diamond

Spectral analysis of electron spin resonance (ESR) is a powerful technique for various investigations including characterization of spin systems, measurements of spin concentration, and probing spin dynamics. The nitrogen-vacancy (NV) center in diamond is a promising magnetic sensor enabling improvement of ESR sensitivity to the level of a single spin. Therefore, understanding the nature of the NV-detected ESR (NV-ESR) spectrum is critical for applications to nanoscale ESR. Within this work, we investigate the linewidth of NV-ESR from single substitutional nitrogen centers (called P1 centers). NV-ESR is detected by a double electron-electron resonance (DEER) technique. By studying the dependence of the DEER excitation bandwidth on the NV-ESR linewidth, we find that the spectral resolution is improved significantly and eventually limited by inhomogeneous broadening of the detected P1 ESR. Moreover, we show that the NV-ESR linewidth can be as narrow as 0.3 MHz.

Highly Anisotropic P3HT Film Fabricated via Epitaxy on an Oriented Polyethylene Film and Solvent Vapor Treatment

To improve the epitaxial crystallization ability of poly(3-hexylthiophene) (P3HT) on a highly oriented polyethylene (PE) substrate, controlled solvent vapor treatment (CSVT) is employed. The anisotropic structures and related optical properties depend not only on the solvent used to prepare the film but also on the subsequent solvent vapor treatment pressure and time. A highly oriented PE film facilitates the "side-on" chain orientation of P3HT with its c axis parallel to the drawing direction of the PE film. The dichroic ratio (DR) of the P3HT film reflected by UV-vis spectra can reach as high as 7.1, which is much larger than the value treated by thermal annealing. Moreover, the excitation bandwidth W, indicating the effective conjugation length and molecular order, shows significant anisotropic features. Solvent used for solution processing with a high boiling point is more favorable for inducing anisotropic multiscale structures. In particular, the oriented structures lead to obvious anisotropic carrier mobility. The carrier mobility of P3HT after CSVT along the PE molecular chain direction is 7.5 times higher than that measured perpendicular to the PE chain direction. This is of great importance in fabricating anisotropic thin films of conjugated polymeric semiconductors with enhanced performance.

Floquet spin and spin-orbital Hamiltonians and doublon-holon generations in periodically driven Mott insulators

We consider Mott insulators driven by periodic coherent laser radiation, using both single orbital and multi-orbital models, noting that the latter is of more interest in solid state systems. We derive general expressions for the resulting periodically driven spin models and spin-orbital models using time-dependent perturbation theory. First, we show that the effective exchange interactions of the Floquet Hamiltonians are highly tunable by the frequency, amplitude, and polarization of the laser. Second, we take the effect of finite bandwidth of excitations into account and study possible heating effects. Using the same formalism with a slight modification we also consider the small frequency regime and study the dielectric breakdown of Mott insulators.

Artefact-free broadband 2D NMR for separation of quadrupolar and paramagnetic shift interactions

Two new two-dimensional, broadband, solid-state NMR experiments for separating and correlating the quadrupolar and shift interactions of spin I=1 nuclei in paramagnetic systems are proposed. The new pulse sequences incorporate the short, high-power adiabatic pulses (SHAPs) into the shifting d-echo experiment of Walder et al. [J. Chem. Phys., 142, 014201 (2015)], in two different ways, giving double and quadruple adiabatic shifting d-echo sequences. These new experiments have the advantage over previous methods of both suppressing spectral artefacts due to pulse imperfections, and exhibiting a broader excitation bandwidth. Both experiments are analysed with theoretical calculations and simulations, and are applied experimentally to the 2H NMR of deuterated CuCl2 ⋅2H2O, and two deuterated samples of the ion conductor oxyhydride BaTiO3−xHy prepared using two different methods. For the CuCl2 ⋅2H2O sample, both new methods obtain very high-quality spectra from which the parameters describing the shift and quadrupolar interaction tensors, and their relative orientation, were extracted. The two BaTiO3−xHy samples exhibited different local hydride environments with different tensor parameters. The 2H spectra of these oxyhydrides exhibit inhomogeneous broadening of the 2H shifts, and so whilst the quadrupolar interaction parameters were easily extracted, the measurement of the shift parameters was more complex. However, effective shift parameters were extracted, which combine the effects of both the paramagnetic shift tensor and the inhomogeneous broadening.

Numerical investigation of spin excitations in a doped spin chain

We study the doping evolution of spin excitations in a 1D Hubbard model and its downfolded spin Hamiltonians, by using exact diagonalization combined with cluster perturbation theory. In all models, we observe hardening (softening) of spin excitations upon electron (hole) doping, which are reminiscent of recent experiments on 2D cuprate materials. We also find that the 3-site and even higher-order terms are crucial for the low-energy effective spin models to reproduce the magnetic spectra of doped Hubbard systems at a quantitative level. To interpret the numerical results, we further employ a strong coupling slave-boson mean-field theory. The mean-field theory provides an intuitive understanding of the overall compact support of dynamic spin structure factors, including the shift of zero-energy modes and change of spin excitation bandwidth with doping. Our results can serve as predictive benchmarks for future inelastic x-ray or neutron scattering experiments on doped 1D antiferromagnetic Mott insulators.

RDEER: A Modified DEER Sequence for Distance Measurements Using Shaped Pulses

The DEER (double electron-electron resonance, also called PELDOR) experiment, which probes the dipolar interaction between two spins and thus reveals distance information, is an important tool for structural studies. In recent years, shaped pump pulses have become a valuable addition to the DEER experiment. Shaped pulses offer an increased excitation bandwidth and the possibility to precisely adjust pulse parameters, which is beneficial especially for demanding biological samples. We have noticed that on our home built W-band spectrometer, the dead-time free 4-pulse DEER sequence with chirped pump pulses suffers from distortions at the end of the DEER trace. Although minor, these are crucial for Gd(III)-Gd(III) DEER where the modulation depth is on the order of a few percent. Here we present a modified DEER sequence—referred to as reversed DEER (rDEER)—that circumvents the coherence pathway which gives rise to the distortion. We compare the rDEER (with two chirped pump pulses) performance values to regular 4-pulse DEER with one monochromatic as well as two chirped pulses and investigate the source of the distortion. We demonstrate the applicability and effectivity of rDEER on three systems, ubiquitin labeled with Gd(III)-DOTA-maleimide (DOTA, 1,4,7,10-Tetraazacyclododecane-1,4,7,10-tetraacetic acid) or with Gd(III)-DO3A (DO3A, 1,4,7,10-Tetraazacyclododecane-1,4,7-triyl) triacetic acid) and the multidrug transporter MdfA, labeled with a Gd(III)-C2 tag, and report an increase in the signal-to-noise ratio in the range of 3 to 7 when comparing the rDEER with two chirped pump pulses to standard 4-pulse DEER.

Poly(3-hexylthiophene) nanowhiskers filler in poly(ε-caprolactone) based nanoblends as potential bioactive material

The inclusion of a polymeric nanofiller with distinctive optoelectronic properties within a well-processable polymer matrix has enabled the fabrication of a wide range of functional materials. However, most of recent works focused on the characterization of the entire composite, without taking into account the effects of the matrix in the morphology of the nanofillers. This paper reports a comprehensive study about the dispersion of poly(3-hexylthiophene) (P3HT) nanowhiskers (NWs) within a poly(ε-caprolactone) (PCL) matrix, yielding a structurally defined nanoblend that could be applied as photoactive material for tissue engineering. NW formation through P3HT crystallization/aggregation was investigated within anisole solutions of PCL by UV-vis spectroscopy, while the excitation bandwidth and the resonant Coulomb coupling constant were calculated by using a non-isothermal variation of the Avrami’s law. The presence of PCL was demonstrated to increase the rate of P3HT crystallization, and determined the assembly of well-defined NWs, featuring a larger conjugation length than that characteristic of nanocrystals obtained from pure P3HT. P3HT-PCL films presented the semicrystalline morphology typical of PCL, with aggregates of P3HT NWs mainly concentrating at the boundaries of PCL spherulites, and thus forming a semiconducting polymer network that expands through a biodegradable polymer matrix.

Defect Detection Studies on Time Reversal Theory in Pipelines

This paper investigates the use of time reversal processing techniques to compensate for multimodal and dispersive effects in a low-power structural health monitoring system for pipelines. We demonstrate the use of time reversal as a pitch-catch operation between two transducer arrays to illuminate changes caused by damage on a pipe. The response is then propagated backwards through the medium from the same array. We demonstrate how this method provides a metric for classifying the magnitude of damage in a pipe while relaxing the restrictions on excitation frequency and bandwidth that are imposed on many other nondestructive techniques.

A parametric resonator with low threshold excitation for vibration energy harvesting

A parametric resonator for vibration energy harvesting is presented. Despite large responses from parametric resonance, two major drawbacks of parametric resonance harvesters are the high threshold excitation and narrow bandwidth. We addressed these two shortcomings by adding magnetic nonlinearity to the system. The proposed vibration energy harvester consists of two piezoelectric cantilevers beams, each with a magnetic tip. By controlling the distance between the two magnets, the threshold excitation level needed to trigger the parametric resonance decreases. Combining the softening and hardening behavior of the two magnetically coupled beams increases the frequency bandwidth. In addition, the amplitude of the response increases with the merger of the direct and parametric resonances of the two beams. We present a mathematical model of the system consisting of two lumped systems coupled by the magnetic force. The coupled governing equations are solved numerically, analytically, and are verified by experiments. Unique characteristics of wider bandwidth, larger response, and lower threshold excitation occur at the low frequency because of the added magnetic nonlinearity to the two-beam system. These properties can improve the efficiency of vibration energy harvesters.

Stochastic Responses for the Vibro‐Impact System under the Broadband Noise

The stochastic averaging is applied to derive the random responses of the SDOF vibro‐impact system with one‐side wall under additive and multiplicative broadband noise, where the impact is described by the modified Hertzian contact model. Compared with the popular simplified “classical model” (i.e., ), the whole impact process is captured by the modified Hertzian contact model without any assumptions. One example is given to illustrate the proposed technique. The comparison between the analytical results and those from Monte Carlo simulations manifests the accuracy of the proposed technique. It should be pointed out that the technique proposed in this paper is powerful for the cases of weak excitation and big enough bandwidth of the broadband noise. Finally, the influences of various parameters are also discussed in detail.

Effect of Electron-Nuclear Hyperfine Interactions on Multiple-Quantum Coherences in Photogenerated Covalent Radical (Qubit) Pairs.

Ultrafast photodriven electron transfer reactions starting from an excited singlet state in an organic donor-acceptor molecule can generate a spin-correlated radical pair (RP) with an initially entangled spin state that may prove useful as a two-qubit pair in quantum information protocols. Here we investigate the effects of modulating electron-nuclear hyperfine coupling by rapidly transferring an electron between two equivalent sites comprising the reduced acceptor of the RP. A covalent electron donor-acceptor molecule including a tetrathiafulvalene (TTF) donor, a 4-aminonaphthalene-1,8-imide (ANI) chromophoric primary acceptor, and an m-xylene bridged cyclophane having two equivalent pyromellitimides (PI2), TTF-ANI-PI2, as a secondary acceptor was synthesized along with an analogous molecule having one pyromellitimide (PI) acceptor, TTF-ANI-PI. Photoexcitation of ANI within each molecule results in sub-nanosecond formation of TTF+•-ANI-PI-• and TTF+•-ANI-PI2-•. The effect of reducing electron-nuclear hyperfine interactions in TTF+•-ANI-PI2-• relative to TTF+•-ANI-PI-• on decoherence of multiple-quantum coherences has been measured by pulse-EPR spectroscopy. This contribution is especially relevant in the absence of modulation of exchange or dipolar interactions, as with the RP at a fixed distance in the molecules in this work. The theoretical prediction of the contribution from an ensemble of hyperfine interactions to decoherence in these RPs is shown to be less than the full width at half-maximum of the quantum beat frequencies measured experimentally. Pulse bandwidth and off-resonant excitation by square microwave pulses are proposed as larger contributors to decoherence in these molecules than the hyperfine interactions, and specific pulse shapes relevant to arbitrary waveform generation are introduced.

Effects of Excitation Bandwidth on Damping Reduction Factor

ABSTRACT In seismic codes, elastic response spectra are usually defined by adopting a conventional value for the damping ratio equal to 5%. Damping Reduction Factors (DRFs) are then introduced to account for the effect of damping values higher than the nominal 5%. In this framework, the main aim of the present study is to explore a new definition of DRF. The concept of stochastic response spectrum is used for predicting the earthquake response of a structural system by adopting the random vibration theory for nonstationary processes. The peak theory is finally used to determine the DRF.

Spin gaps in the ordered states of La2LiXO6(X=Ru,Os) and their relation to the distortion of the cubic double perovskite structure in 4d3 and 5d3 magnets

Time-of-flight inelastic neutron scattering measurements have been carried out on polycrystalline samples of the 4$d^3$ and 5$d^3$ double pervoskite antiferromagnets La$_2$LiRuO$_6$ and La$_2$LiOsO$_6$. These reveal the development of an inelastic spin gap in La$_2$LiRuO$_6$ and La$_2$LiOsO$_6$ of $\sim$ 1.8(8) meV and 6(1) meV, below their respective ordering temperatures, $T_N$, $\sim$ 23.8 K and 30 K. The bandwidth of the spin excitations is shown to be $\sim$ 5.7(9) to 12(1) meV, respectively, at low temperatures. Spin gaps are surprising in such magnets as the t$_{2g}$ levels of Ru$^{5+}$ or Os$^{5+}$ are expected to be half-filled, resulting in an anticipated orbital singlet for both materials. We compare these results in monoclinic double perovskites La$_2$LiRuO$_6$ and La$_2$LiOsO$_6$ with those in cubic Ba$_2$YRuO$_6$ and Ba$_2$YOsO$_6$, as well as with those in the more strongly monoclinic La$_2$NaRuO$_6$, La$_2$NaOsO$_6$, and Sr$_2$ScOsO$_6$, and model the inelastic magnetic scattering with linear spin wave theory using minimal anisotropic exchange interactions. We discuss the possible role of the distortion of the face-centered cubic, double perovskite structure on the spin gap formation and geometric frustration in these materials, and show that $T_N$ scales with the top of the spin wave band in all members of these families that display long range order.

Feedback control optimisation of ESR experiments

Numerically optimised microwave pulses are used to increase excitation efficiency and modulation depth in electron spin resonance experiments performed on a spectrometer equipped with an arbitrary waveform generator. The optimisation procedure is sample-specific and reminiscent of the magnet shimming process used in the early days of nuclear magnetic resonance – an objective function (for example, echo integral in a spin echo experiment) is defined and optimised numerically as a function of the pulse waveform vector using noise-resilient gradient-free methods. We found that the resulting shaped microwave pulses achieve higher excitation bandwidth and better echo modulation depth than the pulse shapes used as the initial guess. Although the method is theoretically less sophisticated than simulation based quantum optimal control techniques, it has the advantage of being free of the linear response approximation; rapid electron spin relaxation also means that the optimisation takes only a few seconds. This makes the procedure fast, convenient, and easy to use. An important application of this method is at the final stage of the implementation of theoretically designed pulse shapes: compensation of pulse distortions introduced by the instrument. The performance is illustrated using spin echo and out-of-phase electron spin echo envelope modulation experiments. Interface code between Bruker SpinJet arbitrary waveform generator and Matlab is included in versions 2.2 and later of the Spinach library.

Improved signal fidelity in 4-pulse DEER with Gaussian pulses

The introduction of arbitrary waveform generator (AWG) technology and the availability of high power microwave amplifiers mark a “new era” in pulse EPR due to significant sensitivity improvements and the possibility to perform novel types of experiments. We present an optimized 4-pulse DEER setup that uses Gaussian observer pulses (GaussDEER) in connection with a Gaussian/shaped pump pulse. Gaussian pulses allow to experimentally remove the “2+1” pulse train ESE signal which is intrinsically present in any DEER experiment performed with rectangular pulses. Further signal improvements are obtained with shaped pump pulses, which can significantly increase the modulation depth of the DEER experiment due to their tailored excitation bandwidth. Although sequences like CP (Carr-Purcell) DEER offer advantages such as a prolongation of the dipolar evolution time, they suffer from post-processing of the time-domain data to remove artifacts. Therefore, it is worth having a 4-pulse DEER experiment free of residual “2+1” signal since this is still the main dipolar spectroscopic technique used in structural biology. In this work we focus on nitroxides, which are the spin probes primarily used in site-directed spin labeling studies of biomolecules, however, the advantages introduced by Gaussian pulses can be extended to any spin type.

Floquet Engineering of Multiorbital Mott Insulators: Applications to Orthorhombic Titanates.

We consider driving multiorbital Mott insulators using laser radiation. We derive general expressions for periodically driven spin-orbital models using time-dependent perturbation theory in the strong interaction limit. We show that the effective exchange interactions of the Floquet spin-orbital Hamiltonian are highly tunable via variations of the frequency, amplitude, and polarization of the laser. We also take the effect of a finite bandwidth of excitations into account and study possible heating effects. We further apply our formalism to orthorhombic titanates YTiO_{3} and LaTiO_{3} based on first-principles calculations, and we find that the spin exchange interactions in these compounds can be engineered to a large extent by tuning the frequency and electric-field amplitude of the laser.

Self-Referencing Luminescence Thermometry with Probes Emitting Red and NIR

Luminescence of any substance is strongly affected by temperature. Therefore, in principle, any material may be utilized to determine temperature from changes in its excitation and emission band energies and bandwidths, emission intensities, ratios of intensities of different emission bands, polarization/anisotropy, emission decay- and rise-times [1, 2]. However, for practical applications in thermometry, materials and material’s systems ought to be thermally and chemically stable, have sufficient brightness and photostability, and their luminescence should notable change with temperature. Today, lanthanide and transition metal activated phosphors, quantum dots, organic dyes and pigments, and metal-organic complexes and frameworks are common choices for luminescence thermometry probes. Among them, due to compatibility with the biological “optical window” and low interference from light scattering and background fluorescence, those probes emitting in the red and near-infrared parts of the electromagnetic spectrum are of exceptional interest for bio-medical applications. Here, the focus is on the emission intensity ratio and emission decay based luminescence thermometry methods because they are self-referencing (do not require reference measurements) and are not affected by changes in measurements conditions. The principle of operation of these methods is presented along with corresponding figures of merit. Then, the main red- and NIR-emitting materials utilized for thermometry probes are listed and their performance is discussed. These include Eu3+, Nd3+, Cr3+ and Mn4+ activated phosphors, PbSe, PbS, CdSe/ZnS and PbS/CdS/ZnS core–shell, ZnS−AgInS2 alloy, ZnS:Mn2+, CsPbCl3:Mn2+ quantum dots, and organic Pluronic F127–Cy5.5 hybrid probe and metal-organic Eu0.0069Tb0.9931-2,5-dimethoxy-1,4-benzenedicarboxylate probes. Finally, several examples of multifunctional applications of these probes and methods is shown, such as in combined bio-imagining and thermal sensing, photothermal therapy and combined physical and chemical sensing.

Indirect detection of broad spectra in solid-state NMR using interleaved DANTE trains

We analyze the performances and the optimization of 1H-{I} HMQC experiments using basic and interleaved DANTE schemes for the indirect detection of nuclei I = 1/2 or 1 exhibiting wide lines dominated by chemical shift anisotropy (CSA) or quadrupole interaction, respectively. These sequences are first described using average Hamiltonian theory. Then, we analyze using numerical simulations (i) the optimal lengths of the DANTE train and the individual pulses, (ii) the robustness of these experiments to offset, and (iii) the optimal choice of the defocusing and refocusing times for both 1H-{I} J- and D-HMQC sequences for 195Pt (I = 1/2) and 14N (I = 1) nuclei subject to large CSA and quadrupole interaction, respectively. These simulations are compared to 1H-{14N} D-HMQC experiments on γ-glycine and L-histidine.HCl at B0 = 18.8 T and MAS frequency of 62.5 kHz. The present study shows that (i) the optimal defocusing and refocusing times do not depend on the chosen DANTE scheme, (ii) the DANTE trains must be applied with the highest rf-field compatible with the probe specifications and the stability of the sample, (iii) the excitation bandwidth along the indirect dimension of HMQC sequence using DANTE trains is inversely proportional to their length, (iv) interleaved DANTE trains increase the excitation bandwidth of these sequences, and (v) dephasing under residual 1H–1H and 1H-I dipolar couplings, as well as 14N second-order quadrupole interaction, during the length of the DANTE scheme attenuate the transfer efficiency.

The effect of laser pulse bandwidth on the measurement of the frequency fluctuation correlation functions in 2D electronic spectroscopy

Several methods have been proposed to obtain the frequency fluctuation correlation function (FFCF) of a transition from the 2DES spectra without complicated fitting procedures. Although all were shown to give correct values in idealized conditions, this might not be applicable in real experimental circumstances. Here, we observe the effects of using different bandwidth excitation pulses in three commonly used methods: ellipticity, center line slope of slices along excitation (CLSω1) and detection (CLSω3) frequencies. The studies were performed on the Qy transition of chlorophyll a. We show that the CLSω3 method gives consistent results for all bandwidths used. For the other two methods, the recovered FFCF values decrease in magnitude with decreasing excitation pulse bandwidths. We also show that by applying the simplified expressions derived by Do et al., incorporating finite pulses in 2DES spectra simulation, we can recover accurate FFCFs using any of these methods.

Effect of electron correlations on spin excitation bandwidth in Ba0.75K0.25Fe2As2 as seen via time-of-flight inelastic neutron scattering

We use inelastic neutron scattering (INS) to investigate the effect of electron correlations on spin dynamics in the iron-based superconductor Ba$_{0.75}$K$_{0.25}$Fe$_{2}$As$_{2}$. Our INS data show a spin-wave-like dispersive feature, with a zone boundary energy of 200 meV. A first principles analysis of dynamical spin susceptibility, incorporating the mass renormalization factor of 3, as determined by angle-resolved photoemission spectroscopy, provides a reasonable description of the observed spin excitations. This analysis shows that electron correlations in the Fe-3$d$ bands yield enhanced effective electron masses, and consequently, induce substantial narrowing of the spin excitation bandwidth. Our results highlight the importance of electron correlations in an itinerant description of the spin excitations in iron-based superconductors.