Peak Line Shape Research Articles

Femtosecond stimulated Raman line shapes: Dependence on resonance conditions of pump and probe pulses

Resonance enhancement has been increasingly employed in the emergent femtosecond stimulated Raman spectroscopy (FSRS) to selectively monitor molecular structure and dynamics with improved spectral and temporal resolutions and signal-to-noise ratios. Such joint efforts by the technique- and application-oriented scientists and engineers have laid the foundation for exploiting the tunable FSRS methodology to investigate a great variety of photosensitive systems and elucidate the underlying functional mechanisms on molecular time scales. During spectral analysis, peak line shapes remain a major concern with an intricate dependence on resonance conditions. Here, we present a comprehensive study of line shapes by tuning the Raman pump wavelength from red to blue side of the ground-state absorption band of the fluorescent dye rhodamine 6G in solution. Distinct line shape patterns in Stokes and anti-Stokes FSRS as well as from the low to high-frequency modes highlight the competition between multiple third-order and higher-order nonlinear pathways, governed by different resonance conditions achieved by Raman pump and probe pulses. In particular, the resonance condition of probe wavelength is revealed to play an important role in generating circular line shape changes through oppositely phased dispersion via hot luminescence (HL) pathways. Meanwhile, on-resonance conditions of the Raman pump could promote excited-state vibrational modes which are broadened and red-shifted from the coincident ground-state vibrational modes, posing challenges for spectral analysis. Certain strategies in tuning the Raman pump and probe to characteristic regions across an electronic transition band are discussed to improve the FSRS usability and versatility as a powerful structural dynamics toolset to advance chemical, physical, materials, and biological sciences.

Vibrational Dynamics and Couplings of the Hydrated RNA Backbone: A Two-Dimensional Infrared Study.

The equilibrium structure of the RNA sugar-phosphate backbone and its hydration shell is distinctly different from hydrated DNA. Applying femtosecond two-dimensional infrared (2D-IR) spectroscopy in a range from 950 to 1300 cm-1, we elucidate the character, dynamics, and couplings of backbone modes of a double-stranded RNA A-helix geometry in its aqueous environment. The 2D-IR spectra display a greater number of backbone modes than for DNA, with distinctly different lineshapes of diagonal peaks. Phosphate-ribose interactions and local hydration structures are reflected in the complex coupling pattern of RNA modes. Interactions with the fluctuating water shell give rise to spectral diffusion on a 300 fs time scale, leading to a quasi-homogeneous line shape of the symmetric (PO2)- stretching mode of the strongly hydrated phosphate groups. The RNA results are benchmarked by 2D-IR spectra of DNA oligomers in water and analyzed by molecular dynamics and quantum mechanical molecular mechanics simulations.

Comprehensive analysis of NMR data using advanced line shape fitting

NMR spectroscopy is uniquely suited for atomic resolution studies of biomolecules such as proteins, nucleic acids and metabolites, since detailed information on structure and dynamics are encoded in positions and line shapes of peaks in NMR spectra. Unfortunately, accurate determination of these parameters is often complicated and time consuming, in part due to the need for different software at the various analysis steps and for validating the results. Here, we present an integrated, cross-platform and open-source software that is significantly more versatile than the typical line shape fitting application. The software is a completely redesigned version of PINT (https://pint-nmr.github.io/PINT/). It features a graphical user interface and includes functionality for peak picking, editing of peak lists and line shape fitting. In addition, the obtained peak intensities can be used directly to extract, for instance, relaxation rates, heteronuclear NOE values and exchange parameters. In contrast to most available software the entire process from spectral visualization to preparation of publication-ready figures is done solely using PINT and often within minutes, thereby, increasing productivity for users of all experience levels. Unique to the software are also the outstanding tools for evaluating the quality of the fitting results and extensive, but easy-to-use, customization of the fitting protocol and graphical output. In this communication, we describe the features of the new version of PINT and benchmark its performance.

Electronic Transport in Bilayer MoS2 Encapsulated in HfO2.

The exact nature of the interface between a two-dimensional crystal and its environment can have a significant impact on the electronic transport within the crystal, and can place fundamental limitations on transistor performance and long-term functionality. Two-dimensional transition-metal dichalcogenides are a new class of transistor channel material with electronic properties that can be tailored through dielectric engineering of the material/environmental interface. Here, we report electrical transport measurements carried out in the insulating regime of bilayer molybdenum disulfide, which has been encapsulated within a high-κ hafnium oxide dielectric. Temperature- and carrier-density-dependent measurements show that for T < 130 K the transport is governed by resonant tunneling, and at T = 4.2 K the tunneling peak lineshape is well-fitted by a Lorentzian with an amplitude less than e2/h. Estimates of tunneling time give τ ∼ 1.2 ps corresponding to a frequency f ∼ 0.84 THz. The tunneling processes are observable up to T ∼ 190 K (more than a factor of 6 higher than that previously reported for MoS2 on SiO2) despite the onset of variable range hopping at T ∼ 130 K, demonstrating the coexistence of the two transport processes within the same temperature range. At constant temperature, varying the Fermi energy allows experimental access to each transport process. The results are interpreted in terms of an increase in charge carrier screening length and a decrease in electron-phonon coupling induced by the hafnium oxide. Our results represent the first demonstration of the intermediate tunneling-hopping transport regime in a two-dimensional material. The results suggest that interface engineering may be a macroscopic tool for controlling quantum transport within such materials as well as for increasing the operating temperatures for resonant-tunneling devices derived from such materials, with applications in high-frequency electronics and logic devices.

Tunable compact nanosensor based on Fano resonance in a plasmonic waveguide system

An ultracompact plasmonic refractive index sensor based on Fano resonance is proposed. The sensor comprises a metal-insulator-metal waveguide with a stub and a side-coupled split-ring resonator. The effect of structural parameters on Fano resonance and the refractive index sensitivity of the system are analyzed in detail by investigating the transmission spectrum. Simulation results show that Fano resonance has different dependences on the parameters of the sensor structure. The reason is further discussed based on the field pattern. The peak wavelength and lineshape can be easily tuned by changing the key parameters. Furthermore, dual Fano resonance effects with different frequency intervals are obtained, which are mainly induced by the symmetry breaking of the structure. The proposed sensor yields sensitivity higher than 1.4×103 nm/RIU and a figure of merit of 1.2×105. The sensitivity and figure of merit can be further improved by optimizing the geometry parameters.

27Al MAS NMR Studies of HBEA Zeolite at Low to High Magnetic Fields

27Al single pulse (SP) MAS NMR spectra of HBEA zeolites with high Si/Al ratios of 71 and 75 were obtained at three magnetic field strengths of 7.05, 11.75, and 19.97 T. High field 27Al MAS NMR spectra acquired at 19.97 T show significantly improved spectral resolution, resulting in at least two well-resolved tetrahedral-Al NMR peaks. Based on the results obtained from 27Al MAS and MQMAS NMR acquired at 19.97 T, four different quadrupole peaks are used to deconvolute the 27Al SP MAS spectra acquired at various fields by using the same set of quadrupole coupling constants, asymmetric parameters and relative integrated peak intensities for the tetrahedral Al peaks. The line shapes of individual peaks change from typical quadrupole line shape at low field to essentially symmetrical line shapes at high field. We demonstrate that, for fully hydrated HBEA zeolites, the effect of second-order quadrupole interaction can be ignored, and quantitative spectral analysis can be performed by directly fitting the high fi...

Structure and Intermolecular Interactions between L-Type Straight Flagellar Filaments

Bacterial mobility is powered by rotation of helical flagellar filaments driven by rotary motors. Flagellin isolated from the Salmonella Typhimurium SJW1660 strain, which differs by a point mutation from the wild-type strain, assembles into straight filaments in which flagellin monomers are arranged in a left-handed helix. Using small-angle x-ray scattering and osmotic stress methods, we investigated the structure of SJW1660 flagellar filaments as well as the intermolecular forces that govern their assembly into dense hexagonal bundles. The scattering data were fitted to models, which took into account the atomic structure of the flagellin subunits. The analysis revealed the exact helical arrangement and the super-helical twist of the flagellin subunits within the filaments. Under osmotic stress, the filaments formed two-dimensional hexagonal bundles. Monte Carlo simulations and continuum theories were used to analyze the scattering data from hexagonal arrays, revealing how the bundle bulk modulus and the deflection length of filaments in the bundles depend on the applied osmotic stress. Scattering data from aligned flagellar bundles confirmed the theoretically predicated structure-factor scattering peak line shape. Quantitative analysis of the measured equation of state of the bundles revealed the contributions of electrostatic, hydration, and elastic interactions to the intermolecular forces associated with bundling of straight semi-flexible flagellar filaments.

时间周期双阱势中光子辅助Dirac电子的Fano共振隧穿

在具有时间周期双阱势的石墨烯体系中，我们研究了光子辅助Dirac电子的Fano型共振隧穿。研究结果表明，由于双阱势中束缚态能级的劈裂，Fano型共振谱会分裂成两个不对称的共振峰。这两个非对称Fano型共振峰的形状不同。并且，两个振荡场的相对相位可以调制非对称Fano型共振峰的形状。此外，我们还可以通过改变振荡场的频率、振幅以及静势阱的结构来调制Fano峰的轮廓。 The photon-assisted Fano-type resonance transmission of a Dirac electron through a time-periodic double-well potential in graphene is investigated. It is shown that the Fano-type resonance spectra through double wells are divided into two asymmetric resonance peaks due to the level splitting of bound state in double wells. The line shapes of two asymmetric Fano-type resonance peaks are different. Moreover, the relative phase of the two oscillating fields can adjust the line shapes of the asymmetry Fano-type resonance peaks. Additionally, the profile of Fano-type resonance can be also controlled by adjusting the frequency and amplitude of the applied oscillating fields, and the structure of the static quantum wells.

Perturbation Approach for Computing Infrared Spectra of the Local Mode of Probe Molecules.

Linear and two-dimensional infrared (IR) spectroscopy of site-specific probe molecules provides an opportunity to gain a molecular-level understanding of the local hydrogen-bonding network, conformational dynamics, and long-range electrostatic interactions in condensed-phase and biological systems. A challenge in computation is to determine the time-dependent vibrational frequencies that incorporate explicitly both nuclear quantum effects of vibrational motions and an electronic structural representation of the potential energy surface. In this paper, a nuclear quantum vibrational perturbation (QVP) method is described for efficiently determining the instantaneous vibrational frequency of a chromophore in molecular dynamics simulations. Computational efficiency is achieved through the use of (a) discrete variable representation of the vibrational wave functions, (b) a perturbation theory to evaluate the vibrational energy shifts due to solvent dynamic fluctuations, and (c) a combined QM/MM potential for the systems. It was found that first-order perturbation is sufficiently accurate, enabling time-dependent vibrational frequencies to be obtained on the fly in molecular dynamics. The QVP method is illustrated in the mode-specific linear and 2D-IR spectra of the H-Cl stretching frequency in the HCl-water clusters and the carbonyl stretching vibration of acetone in aqueous solution. To further reduce computational cost, a hybrid strategy was proposed, and it was found that the computed vibrational spectral peak position and line shape are in agreement with experimental results. In addition, it was found that anharmonicity is significant in the H-Cl stretching mode, and hydrogen-bonding interactions further enhance anharmonic effects. The present QVP method complements other computational approaches, including path integral-based molecular dynamics, and represents a major improvement over the electrostatics-based spectroscopic mapping procedures.

Resonant interactions between discrete phonons in quinhydrone driven by nonlinear electron-phonon coupling

This study reports experimental, computational, and theoretical evidence for a previously unobserved coherent phonon-phonon interaction in an organic solid that can be described by the application of Fano's analysis to a case without the presence of a continuum. Using Raman spectroscopy of the hydrogen-bonded charge-transfer material quinhydrone, two peaks appear near $700{\mathrm{cm}}^{\ensuremath{-}1}$ we assign as phonons whose position and line-shape asymmetry depend on the sample temperature and light scattering excitation energy. Density functional theory calculations find two nearly degenerate phonons possessing frequencies near the values found in experiment that share similar atomic motion out of the aromatic plane of electron donor and acceptor molecules of quinhydrone. Further analytical modeling of the steady-state light scattering process using the Peierls-Hubbard Hamiltonian and time-dependent perturbation theory motivates assignment of the physical origin of the asymmetric features of each peak's line shape to an interaction between two discrete phonons via nonlinear electron-phonon coupling. In the context of analytical model results, characteristics of the experimental spectra upon 2.33 eV excitation of the Raman scattering process are used to qualify the temperature dependence of the magnitude of this coupling in the valence band of quinhydrone. These results broaden the range of phonon-phonon interactions in materials in general while also highlighting the rich physics and fundamental attributes specific to organic solids that may determine their applicability in next generation electronics and photonics technologies.

Optical properties of surfaces with supercellab initiocalculations: Local-field effects

Surface optical and electronic properties are crucial for material science and have implications in fields as various as nanotechnology, nonlinear optics, and spectroscopies. In particular, the huge variation of electronic density perpendicular to the surface is expected to play a key role in absorption due to local-field effects. Numerous state-of-the-art theoretical and numerical ab initio formalisms developed for studying these properties are based on supercell approaches, in reciprocal space, due to their efficiency. In this paper, we show that the standard scheme fails for the out-of-plane optical response of the surface. This response is interpreted using the ``effective-medium theory'' with vacuum and also in terms of interaction between replicas, as the supercell approach implies a periodicity which is absent in the real system. We propose an alternative formulation, also based on the supercell, for computing the macroscopic dielectric function. Application to the clean Si(001) $2\ifmmode\times\else\texttimes\fi{}1$ surface allows us to present the effect of the local fields for both peak positions and line shape on the bulk and surface contributions. It shows how local fields built up for the in-plane and out-of-plane dielectric responses of the surface. In addition to their conceptual impact, our results explain why the standard approach gives reliable predictions for the in-plane components, leading to correct reflectance anisotropy spectra. Our scheme can be further generalized to other low-dimensional geometries, such as clusters or nanowires, and open the way to nonlinear optics for surfaces.

Optical nonlinearities of small polarons in lithium niobate

An overview of optical nonlinearities of small bound polarons is given, which can occur in the congruently melting composition of LiNbO3. Such polarons decisively influence the linear and nonlinear optical performance of this material that is important for the field of optics and photonics. On the basis of an elementary phenomenological approach, the localization of carriers in a periodic lattice with intrinsic defects is introduced. It is applied to describe the binding energies of four electron and hole small polarons in LiNbO3: small free NbNb4+ polarons, small bound NbLi4+ polarons, small bound NbLi4+:NbNb4+ bipolarons, and small bound O− hole polarons. For the understanding of their linear interaction with light, an optically induced transfer between nearest-neighboring polaronic sites is assumed. It reveals spectrally well separated optical absorption features in the visible and near-infrared spectral range, their small polaron peak energies and lineshapes. Nonlinear interaction of light is assigned to the optical formation of short-lived small polarons as a result of carrier excitation by means of band-to-band transitions. It is accompanied by the appearance of a transient absorption being spectrally constituted by the individual fingerprints of the small polarons involved. The relaxation dynamics of the transients is thermally activated and characterized phenomenologically by a stretched exponential behavior, according to incoherent 3D small polaron hopping between regular and defect sites of the crystal lattice. It is shown that the analysis of the dynamics is a useful tool for revealing the recombination processes between small polarons of different charge. Nonlinear interaction of small polarons with light furthermore results in changes of the index of refraction. Besides its causal relation to the transients via Kramers-Kronig relation, pronounced index changes may occur due to optically generated electric fields modulating the index of refraction via the linear electro-optic effect, also. Based on a microscopic picture and by considering the local structural environment of bound polarons, the appearance of photovoltaic currents is explained straightforwardly as a result of the optically induced carrier transfer. Both transient absorption and index changes are spatially confined to the intensity profile of the interacting light allowing for the recording of efficient mixed absorption and phase volume holograms. By means of holographic spectroscopy, these small-polaron based optical nonlinearities are verified either without or with the action of the linear electro-optic effect; their prominent features are highlighted by appropriate experimental studies wherin the ultrafast response on the picosecond time scale is the most recognized one. Based on these findings, the consequences for applications of LiNbO3 in the field of nonlinear optics and photonics are presented. Besides visionary examples like real-time, 3D holographic displays, the impact of optical nonlinearities of small polarons for present applications are discussed with frequency conversion and respective limiting effects, such as green-induced infrared absorption and optical damage, as important example.

Spin-dependent coherent transport in a double quantum dot system

We study spin-resolved resonant tunneling in a system of two quantum dots sandwiched between doped quantum wells. In the coherent (Dicke) regime, i.e., when quantum dot separation is smaller than the Fermi wavelength in a two-dimensional electron gas in quantum wells, application of an in-plane magnetic field leads to a pronounced spin-resolved structure of the conductance peak lineshape even for very small Zeeman splitting of the quantum dots' resonant levels. In the presence of electron-gas spin-orbit coupling, this spin-resolved structure gets washed out due to Fermi surface deformation in the momentum space. We also show that Aharonov-Bohm flux penetrating the area enclosed by electron tunneling pathways completely destroys conductance spin structure.

Effect of temperature and micro-morphology on the Ag Raman peak in nanocrystalline CuO thin films

Raman spectra obtained from a nanocrystalline CuO thin film are observed to exhibit significant variation in the peak position and peak line-shape as a function of spatial position within the film. We attribute this effect to variation in the degree of local heating beneath the focused spot of the Raman probe laser. To understand this, we have undertaken a detailed study of the temperature-dependence of the CuO Ag Raman peak. We observe a linear relationship between line-width and peak position, which persists over a wide temperature range, and is characteristic of a Raman process in which the temperature-dependence is dominated by anharmonic 3-phonon decay. We provide an analytical description of the Raman line-shape as a function of temperature and use this model to interpret the degree of laser heating observed within our sample. Using this relationship, we identify that the local micro-morphology of the CuO sample under study can dramatically affect the temperature achieved due to laser heating. We find that spectra collected from the surface of “micro-bubbles” within the CuO film studied can reach temperatures of &amp;gt;1000 K beneath the focused spot of our low power (5 mW) probe laser.

Line shape and composition of the In 3d5/2 core-level photoemission for the interface analysis of In-containing III–V semiconductors

The In 3d5/2 photoelectron spectroscopy peak has been widely used to determine the interface structures of In-containing III–V device materials (e.g., oxidation states). However, an unclear parameter affecting the determination of the energy shifts and number of the core-level components, and therefore, the interpreted interface structure and composition, is still the intrinsic In 3d5/2 peak line shape. It is undecided whether the line shape is naturally symmetric or asymmetric for pure In-containing III–V compounds. By using high-resolution photoelectron spectroscopy, we show that the In 3d5/2 asymmetry arising from the emission at high binding-energy tail is not an intrinsic property of InAs, InP, InSb and InGaAs. Furthermore, it is shown that asymmetry of In 3d5/2 peaks of pure III–V's originates from the natural surface reconstructions which cause the coexistence of slightly shifted In 3d5/2 components with the symmetric peak shape and dominant Lorentzian broadening.

Magnetic field-induced direct–indirect crossover in AlxGa1−xAs

We induce a direct–indirect band gap crossover in a single AlxGa1−xAs sample by using high magnetic fields. A reduction in the photoluminescence (PL) peak energy and onset of an asymmetric peak lineshape at magnetic fields >38 T result from a competition between the radiative recombination lifetime and the carrier migration time as the alloy becomes indirect. By analyzing the progression of the PL lineshape as the magnetic field is increased we show that the crossover is an alloy disorder-broadened, first-order phase transition.

Two-Dimensional Ag Nanoparticle Tetramer Array for Surface-Enhanced Raman Scattering Measurements

A two-dimensional Ag nanoparticle tetramer array which served as a hotspot matrix for surface-enhanced Raman scattering detection of rhodamine 6G (R6G) molecules down to a concentration as low as 10–15 M was successfully fabricated by electrochemical deposition on an anodized aluminum substrate. The high detection sensitivity was attributed to both the electromagetic enhancement at the dense Ag nanoparticle tetramer hotspot matrix and chemical enhancement on the corrugated substrate. A single molecule dynamic adsorption behavior was experimentally sensed by the abrupt changes of the charateristic peak intensity and line shape in the spectroscopy when the R6G concentration was lowered to 10–15 M. Time-evolved spectroscopies revealed the adsorption behavior of either the single molecule in the nanogaps of 2–5 nm or multiple molecules in the nanogaps of 5–9 nm between the Ag nanoparticles.

Enhanced Raman scattering of graphene on Ag nanoislands

The effect of Ag nanoislands on the Raman of graphene was investigated in this work. Compared with that on the bare silicon wafer, Raman enhancement was observed in the graphene film that covered on Ag/Si surface with nanoscale Ag islands, which would be induced by the localized plasmon resonance in Ag nanostructures. The interaction between the graphene sheet and Ag/Si substrate was further studied. The peak shift and line shape of Raman spectroscopy indicated a nonuniform strain distribution in the Ag/Si supported graphene film.

Instability of structural defects generated by electron irradiation in GaInNAs quantum wells

Electron irradiation is found to cause a large blue shift of photoluminescence from a 1.3-μm laser-like strain-compensated GaInNAs/GaNAs/GaAs quantum well structure when annealed after irradiation. The line shift is assigned to the presence of complex defect centers in the quantum wells. The defects are very unstable. The peak position and line shape of the spectra are restored to their original values by an ageing effect, which occurs even at room temperature. The mechanism causing the blue shift/red shift of photoluminescence is qualitatively described.

Optical properties of amorphous Ge1−x Se x and Ge1−x−y Se x As y thin films — optical gap bowing and phonon modes

We investigated the optical properties of Ge1−x Se x and Ge1−x−y Se x As y amorphous films by using spectroscopic ellipsometry and Raman spectroscopy. The dielectric functions and absorption coefficients (α) of the amorphous films were determined from the measured ellipsometric angles (Ψ,Δ). We obtained the optical gap energies and the Urbach energies from the absorption coefficients and found a strong bowing effect in the optical gap energy of Ge1−x−y Se x As y , where the endpoint binaries were Ge0.50Se0.50 and Ge0.31As0.69. Based on the correlation between the optical gap energies and the Urbach energies, we attributed the large bowing parameter to electronic disorder. Using Raman spectroscopy, we measured the phonon modes and discussed the composition dependence of the phonon peak frequencies and lineshapes in terms of structural units. Based on the composition dependence of the phonons in Ge1−x−y Se x As y , we identified the phonon modes of Ge0.31As0.69. A resonant Raman phenomenon was observed in Ge0.40Se0.60 at a laser excitation of 514 nm (2.41 eV). We verified that this laser energy corresponded to the transition energy of Ge0.40Se0.60 by using the second derivative of the dielectric function of Ge0.40Se0.60.