Monochromatic Pulses Research Articles

Transverse interference peaks in chirp FT-EPR correlated three-pulse ESEEM spectra

Fourier transform (FT) electron paramagnetic resonance (EPR) correlation spectroscopy usually requires broader excitation bandwidth than can be achieved by monochromatic rectangular pulses. Replacement of such pulses by frequency-swept pulses affords the correlation spectra, which, however, may not look the same as those that would be obtained with sufficiently broad-banded monochromatic rectangular pulses. This was recently observed for correlating nuclear frequencies to FT-EPR spectra by a three-pulse electron spin echo envelope modulation experiment. Here we analyze the origin of the additional cross peaks, whose position depends on the direction of the frequency sweep. We find that such peaks arise if coherence or polarization is transferred to an electron spin transition already before this transition is actually passed during the frequency sweep. This happens by excitation of a chain of transitions that connect levels of the source transition, where coherence resides before mixing, and the target transition, where it resides after mixing. The correlation spectra can be simplified by combining data from frequency up and down sweeps.

Pump-probe spectrometer for measuring x-ray induced strain.

A hard x-ray pump-probe spectrometer using a multi-crystal Bragg reflector is demonstrated at a third generation synchrotron source. This device derives both broadband pump and monochromatic probe pulses directly from a single intense, broadband x-ray pulse centered at 8.767 keV. We present a proof-of-concept experiment which directly measures x-ray induced crystalline lattice strain.

EPR-correlated dipolar spectroscopy by Q-band chirp SIFTER.

While two-dimensional correlation spectra contain more information as compared to one-dimensional spectra, typical spectral widths encountered in electron paramagnetic resonance (EPR) spectroscopy largely restrict the applicability of correlation techniques. In essence, the monochromatic excitation pulses established in pulsed EPR often cannot uniformly excite the entire spectrum. Here, this restriction is alleviated for nitroxide spin labels at Q-band microwave frequencies around 35 GHz. This is achieved by substitution of monochromatic pulses by frequency-swept chirp pulses tailored for uniform excitation. Unwanted interference effects brought by this substitution are analyzed for a pair of electron spins with secular dipolar coupling. Experimentally, the dipole-dipole interaction can be separated from other interactions by a constant-time Zeeman-compensated solid echo sequence called SIFTER. Such SIFTER experiments usually yield a one-dimensional dipolar spectrum. EPR-correlated dipolar spectra can be obtained when the four pulses are replaced by chirp pulses. These two-dimensional spectra encode additional information on the geometrical arrangement of the two spin labels. With the excitation parameters achieved by a home-built Q-band spectrometer capable of frequency-swept excitation, unwanted interference effects can be largely neglected for the examined model compound with a spin-spin distance of 4 nm. The experimentally obtained correlation pattern conforms to the expectation based on the inter-spin geometry of the investigated rigid model compound.

Theory for spiralling ions for 2D FT-ICR and comparison with precessing magnetization vectors in 2D NMR.

Two-dimensional (2D) Fourier transform ion cyclotron resonance (FT-ICR) offers an approach to mass spectrometry (MS) that pursuits similar objectives as MS/MS experiments. While the latter must focus on one ion species at a time, 2D FT ICR can examine all possible correlations due to ion fragmentation in a single experiment: correlations between precursors, charged and neutral fragments. We revisited the original 2D FT-ICR experiment that has hitherto fallen short of stimulating significant analytical applications, probably because it is technically demanding. These shortcomings can now be overcome by improved FT-ICR instrumentation and computer hard- and software. We seek to achieve a better understanding of the intricacies of the behavior of ions during a basic two-dimensional ICR sequence comprising three simple monochromatic pulses. Through simulations based on Lorentzian equations, we have mapped the ion trajectories for different pulse durations and phases.

Effects of self-seeding and crystal post-selection on the quality of Monte Carlo-integrated SFX data.

Serial femtosecond crystallography (SFX) is an emerging method for data collection at free-electron lasers (FELs) in which single diffraction snapshots are taken from a large number of crystals. The partial intensities collected in this way are then combined in a scheme called Monte Carlo integration, which provides the full diffraction intensities. However, apart from having to perform this merging, the Monte Carlo integration must also average out all variations in crystal quality, crystal size, X-ray beam properties and other factors, necessitating data collection from thousands of crystals. Because the pulses provided by FELs running in the typical self-amplified spontaneous emission (SASE) mode of operation have very irregular, spiky spectra that vary strongly from pulse to pulse, it has been suggested that this is an important source of variation contributing to inaccuracies in the intensities, and that, by using monochromatic pulses produced through a process called self-seeding, fewer images might be needed for Monte Carlo integration to converge, resulting in more accurate data. This paper reports the results of two experiments performed at the Linac Coherent Light Source in which data collected in both SASE and self-seeded mode were compared. Importantly, no improvement attributable to the use of self-seeding was detected. In addition, other possible sources of variation that affect SFX data quality were investigated, such as crystal-to-crystal variations reflected in the unit-cell parameters; however, these factors were found to have no influence on data quality either. Possibly, there is another source of variation as yet undetected that affects SFX data quality much more than any of the factors investigated here.

Sensitivity enhancement by population transfer in Gd(III) spin labels.

In order to enhance echo signals observed with selective pulses, equilibrium populations of the energy levels of S = 7/2 Gd(III) spin labels are rearranged with frequency-swept passage pulses. To transfer population from as many energy levels as possible, the 2 μs long passage pulses range over more than 1 GHz. Application of this technique at Q-band frequencies to three different Gd(III) complexes and spin dynamics simulations reveal large signal enhancements beyond 100% for Gd(III) complexes with zero-field splitting parameters below 1 GHz. For complexes with larger splittings, experimental enhancements are on the order of 90%. Moreover, population transfer is combined with distance measurements on a model system with a pair of Gd(III) ions. As a result, a signal enhancement of 85% is achieved without inducing changes in the obtained distance information. Besides this enhancement by population transfer, a dipolar modulation depth of 9% is demonstrated, which results in a total enhancement of 3.3 with respect to data obtained with monochromatic rectangular pulses. The limitations of the population transfer technique are discussed. In particular, the extraordinary broad pulse bandwidths caused heating effects and pulse distortions, which constrain the pulse length and thus the achievable signal enhancement.

Time-resolved photoemission apparatus achieving sub-20-meV energy resolution and high stability

The paper describes a time- and angle-resolved photoemission apparatus consisting of a hemispherical analyzer and a pulsed laser source. We demonstrate 1.48-eV pump and 5.92-eV probe measurements at the ⩾10.5-meV and ⩾240-fs resolutions by use of fairly monochromatic 170-fs pulses delivered from a regeneratively amplified Ti:sapphire laser system operating typically at 250 kHz. The apparatus is capable to resolve the optically filled superconducting peak in the unoccupied states of a cuprate superconductor, Bi2Sr2CaCu2O(8 + δ). A dataset recorded on Bi(111) surface is also presented. Technical descriptions include the followings: A simple procedure to fine-tune the spatio-temporal overlap of the pump-and-probe beams and their diameters; achieving a long-term stability of the system that enables a normalization-free dataset acquisition; changing the repetition rate by utilizing acoustic optical modulator and frequency-division circuit.

Direct electron acceleration in plasma waveguides for compact high-repetition-rate x-ray sources

Numerous applications in fundamental and applied research, security, and industry require robust, compact sources of x-rays, with a particular recent interest in monochromatic, spatially coherent, and ultrafast x-ray pulses in well-collimated beams. Such x-ray sources usually require production of high-quality electron beams from compact accelerators. Guiding a radially polarized laser pulse in a plasma waveguide has been proposed for realizing direct laser acceleration (DLA), where the electrons are accelerated by the axial electric field of a co-propagating laser pulse (Serafim et al 2000 IEEE Trans. Plasma Sci. 28 1190). A moderate laser peak power is required for DLA when compared to laser wakefield acceleration, thus offering the prospect for high repetition rate operation. By using a density-modulated plasma waveguide for DLA, the acceleration distance can be extended with pulse guiding, while the density-modulation with proper axial structure can realize the quasi-phase matching between the laser pulses and electrons for a net gain accumulation (York et al 2008 Phys. Rev. Lett. 100 195001; York et al 2008 J. Opt. Soc. Am. B 25 B137; Palastro et al 2008 Phys. Rev. E 77 036405). We describe the development and application of a test particle model and particle-in-cell model for DLA. Experimental setups designed for fabrication of optically tailored plasma waveguides via the ignitor-heater scheme, and for generation and characterization of radially polarized short pulses used to drive DLA, are presented.

Interferences and asymmetries in laser-assisted photoionization of diatomic molecules

Fil: Boll, Diego I. R.. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Rosario. Instituto de Fisica de Rosario (i); Argentina

Interferences in laser assisted photoionization of diatomic molecules

We analyze interference effects in photoionization of H+2 molecular targets in laser assisted photoionization. By means of a simple model, we obtain observables for the reaction and we compare them with previous results obtained with more elaborated ones. Interestingly, previous interference effects predicted for monochromatic pulses persist in the presence of a laser NIR bath leading to a characteristic photoelectron spectrum.

Focusing XFEL SASE pulses by rotationally parabolic refractive x-ray lenses

Using rotationally parabolic refractive x-ray lenses made of beryllium, we focus hard x-ray free-electron laser pulses of the Linac Coherent Light Source (LCLS) down to a spot size in the 100 nm range. We demonstrated efficient nanofocusing and characterized the nanofocused wave field by ptychographic imaging [A. Schropp, et al., Sci. Rep. 3, 1633 (2013)] in the case of monochromatic LCLS pulses produced by a crystal monochromator that decreases the LCLS bandwidth down to ΔE/E = 1.4 · 10−4. The full spectrum of LCLS pulses generated by self-amplified spontaneous emission (SASE), however, fluctuates and has a typical bandwidth of a few per mille (ΔE/E ≈ 2 · 10−3). Due to the dispersion in the lens material, a polychromatic nanobeam generated by refractive x-ray lenses is affected by chromatic aberration. After reviewing the chromaticity of refractive x-ray lenses, we discuss the influence of increased bandwidth on the quality of a nanofocused SASE pulse.

Monochromatic short pulse laser produced ion beam using a compact passive magnetic device.

High-intensity laser accelerated protons and ions are emerging sources with complementary characteristics to those of conventional sources, namely high charge, high current, and short bunch duration, and therefore can be useful for dedicated applications. However, these beams exhibit a broadband energy spectrum when, for some experiments, monoenergetic beams are required. We present here an adaptation of conventional chicane devices in a compact form (10 cm × 20 cm) which enables selection of a specific energy interval from the broadband spectrum. This is achieved by employing magnetic fields to bend the trajectory of the laser produced proton beam through two slits in order to select the minimum and maximum beam energy. The device enables a production of a high current, short duration source with a reproducible output spectrum from short pulse laser produced charged particle beams.

IDEEAA: A novel, versatile apparatus for electron spectroscopy

We report the development and present status of the iDEEAA (Instrument for Direct Electron Energy and Angular Analysis) experimental end station for time- and angle-resolved X-ray photoelectron spectroscopy. The setup is based on multidimensional detection of photoelectrons by means of both time-of-flight (TOF) and/or electrostatic analyzers. The instrument offers the possibility to record simultaneously and independently photoelectron and Auger electron spectra. Samples can be either gases or solids. The system can operate with multiple photon sources, such as laboratory-based table-top laser extreme ultraviolet (EUV) sources, monochromatic Helium discharge lamp and soft X-ray synchrotron pulses. We demonstrate the performance of the setup by carrying out electron–electron coincidence experiments on CH4 and by mapping the band structure of Bi2Se3 using photons of the BESSY II electron storage ring.

Broadband excitation by chirped pulses: application to single electron spins in diamond

Pulsed excitation of broad spectra requires very high field strengths if monochromatic pulses are used. If the corresponding high power is not available or not desirable, the pulses can be replaced by suitable low-power pulses that distribute the power over a wider bandwidth. As a simple case, we use microwave pulses with a linear frequency chirp. We use these pulses to excite spectra of single nitrogen–vacancy centres in a Ramsey experiment. Compared to the conventional Ramsey experiment, our approach increases the bandwidth by at least an order of magnitude. Compared to the conventional continuous wave-ODMR experiment, the chirped Ramsey experiment does not suffer from power broadening and increases the resolution by at least an order of magnitude. As an additional benefit, the chirped Ramsey spectrum contains not only ‘allowed’ single quantum transitions, but also ‘forbidden’ zero- and double quantum transitions, which can be distinguished from the single quantum transitions by phase-shifting the readout pulse with respect to the excitation pulse or by variation of the external magnetic field strength.

Hard x-ray absorption spectroscopy for pulsed sources

We present a method suitable for the measurement of a high-energy resolved absorption spectrum in the emission mode upon target excitation with an intense monochromatic pulse of x-ray light. The approach is based on a measurement of a single resonant Raman x-ray spectrum at a fixed off-resonant excitation energy by a dispersive-type high-resolution emission spectrometer. Using a simple Lorentzian tail correction function and an energy-scale transformation, we reconstructed the ${L}_{3}$ absorption edge of Xe from the $3d$-$2{p}_{3/2}$ resonant Raman x-ray spectrum recorded at excitation energy 25 eV below the ${L}_{3}$ edge. The energy resolution is well below the ${L}_{3}$ core-hole lifetime broadening and allows for a straightforward extraction of the $[2{p}_{3/2}]n\ensuremath{\ell}$ resonance energies and emission strengths. The reconstructed spectrum is nearly equivalent to the high-energy resolution fluorescence detected absorption spectrum, which is recorded by scanning the photon excitation energy across the absorption edge.

Probing IR-Raman vibrationally excited molecules with X-ray spectroscopy

We present detailed calculations of a new scheme for time control of bond dissociation. The scheme combines far-off-resonant Raman transitions [1] initiated by one chirped and one monochromatic laser pulse, with X-ray spectroscopy. The Raman Chirped Adiabatic Passage technique (RCAP) is used to climb vibrational ladders in molecular systems while X-ray interactions act as a probe to follow the change of core binding energy.

Testing the equivalence between the canonical and Minkowski momentum of light with ultracold atoms

We design an experimental system to test the equivalence between the canonical and Minkowski momentum of light, which can provide a judgment on the recent resolution of the century-old Abraham-Minkowski controversy by S. M. Barnett [Phys. Rev. Lett. 104, 070401 (2010)]. By measuring the recoil momentum of ultracold rubidium atoms in a rubidium Bose-Einstein condensate after the electromagnetically induced absorption of a monochromatic laser pulse, the momentum of the pulse in the ultracold atoms can be obtained. If the equivalence is valid, the measured results will coincide with the theoretical values of the canonical momentum of the pulse. Otherwise, if the equivalence is invalid, the measured results will coincide with the theoretical values of the Minkowski momentum, which are significantly different from that of the canonical momentum. Our scheme is amethod to test the equivalence between the canonical and Minkowski momentum of light. It can also be improved to distinguish between the Minkowski and Abraham momenta to contribute to the study of the Abraham-Minkowski controversy in the future.

CEP ef fects on monochromatic high frequency pulse generation from Thomson backscattering

Carrier-envelope phase effect of the monochromatic high frequency pulse generation from Thomson backscattering is investigated with an analytical model and verified by one dimensional particle in cell simulations. We show that the central frequency of the monochromatic light generated from Thomson backscattering is extremely sensitive to the carrier-envelope phase of the field driving the relativistic electron layers.

Development of ultrafast spectroscopic techniques to study rapid chemical and physical changes in materials under extreme pressure and temperature conditions

ABSTRACTIn the study of materials at extreme pressures and temperatures, there is an enduring need to extend the range of experiments to previously inaccessible regimes. To accomplish this, improvements in diagnostics for in situ material characterization at extremes must proceed in parallel with techniques used to generate extreme states. Simultaneously, there is a need to study material phenomena – e.g. phase transformations and chemical reactions triggered by the application of extreme conditions – on their natural timescales. Here we report on recent developments in the application of ultrafast laser spectroscopic techniques to high-pressure hightemperature experiments on materials confined in a diamond-anvil cell. Using a bright broadband source coupled to ultrafast detection to discriminate signal from high thermal and fluorescent backgrounds, we conducted broadband optical spectroscopy up to 60 GPa and 1560 K. By coupling the broadband source to a monochromatic pulse, nonlinear Coherent Anti- Stokes Raman Spectroscopy (CARS) with high signal brightness was achieved. Optical absorption data in hot compressed O2 and CARS data in N2 at extreme pressures are reported.

Inverse Raman bands in ultrafast Raman loss spectroscopy

Ultrafast Raman loss spectroscopy (URLS) is equivalent to anti-Stokes femtosecond stimulated Raman spectroscopy (FSRS), using a broadband probe pulse that extends to the blue of the narrow bandwidth Raman pump, and can be described as inverse Raman scattering (IRS). Using the Feynman dual time-line diagram, the third-order polarization for IRS with finite pulses can be written down in terms of a four-time correlation function. An analytic expression is obtained for the latter in the harmonic approximation which facilitates computation. We simulated the URLS of crystal violet (CV) for various resonance Raman pump excitation wavelengths using the IRS polarization expression with finite pulses. The calculated results agreed well with the experimental results of S. Umapathy et al., J. Chem. Phys. 133, 024505 (2010). In the limit of monochromatic Raman pump and probe pulses, we obtain the third-order susceptibility for multi-modes, and for a single mode we recover the well-known expression for the third-order susceptibility, χ(IRS) ((3)), for IRS. The latter is used to understand the mode dependent phase changes as a function of Raman pump excitation in the URLS of CV.