Line Shape Model Research Articles

Temperature dependence of line shape parameters for N2- and O2-broadened methane lines by quantum cascade laser spectroscopy

This paper report nitrogen- and oxygen-broadening coefficients, their speed-dependencies, and the collisional narrowing parameters of lines in the ν4-band of methane. The parameters were determined from low (150 K) to high temperatures (600 K). The measurements were done with a high-resolution quantum cascade laser spectrometer coupled to specific absorption cells that allow to cool and heat the gas mixtures with a great stability. The spectroscopic parameters were determined at each temperature by fits of the experimental absorbances in a multispectrum fitting procedure using the Voigt, Speed-Dependent Voigt, Nelkin-Ghatak and Speed-dependent Nelkin-Ghatak theoretical line shape models. The temperature dependencies of the collisional half-widths, the speed-dependence of the broadening coefficients as well as the collisional narrowing parameters were studied with the empirical power law and the physics-based Gamache-Vispoel model (DPL) [Gamache and Vispoel, JQSRT, 217, 440–452, 2018]. The obtained line shape parameters and their temperature dependencies are compared, when possible, to existing data in literature. The DPL reproduces more accurately the evolution of the studied collisional parameters over the wide range of temperature considered in the study.

Mid-infrared high-resolution dual-comb spectroscopy: Intensity, broadening, and beyond-Voigt parameters of [formula omitted] and [formula omitted] lines

Using a high-resolution mid-infrared dual-comb spectrometer operating in the 1300 cm−1 spectral region, spectra of acetylene were recorded at room temperature. Spectroscopic parameters were measured in 3 vibrational bands of both 12C2H2 and 13C12CH2. Absolute line intensities (S0) and self-broadening coefficients (γ0self) were determined in the ν4+ν5, 2ν42+ν5−1⟵ν41 and ν41+2ν50⟵ν51 bands. For the main isotopologue, the collisional narrowing coefficients (ν0VC) as well as the speed-dependence of the broadening (γ2) and shifting (δ2) coefficients were measured in the ν4+ν5 band of the main isotopologue of acetylene. Theoretical line-shape models were fitted on experimental profiles using a homemade multi-spectrum fitting procedure to determine spectroscopic parameters. Excellent agreement with the literature was found for self-broadening coefficients and absolute line intensities in the ν4+ν5 band of 12C2H2. For the hot bands, good agreement with the literature is found within experimental uncertainties, while γ0self of those hot bands are also reported for the first time. Similarly, the rotational dependence of ν0VC is found to be close to previous works. γ2 and δ2 of 12C2H2, as well as S0 and γ0self of 13C12CH2 are also reported for the first time in this band.

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Hot Carrier Temperature Dynamics in Semiconductor Nanostructures: Full Lineshape Modeling of Ultrafast Time-Resolved Emission Spectra

Spectral profile of ro-vibrational transitions of HCl broadened by He, Ar and SF6: Testing the β-correction to the Hartmann-Tran profile and the speed dependent (complex) hard collision model

The β-correction to the Hartmann-Tran (HT) profile, recently introduced to model the spectral shape of a molecular transition strongly affected by the Dicke narrowing effect (Konefal et al., JQSRT 242 (2020) 106,784), the HT profile (Ngo et al., JQSRT 129 (2013) 89), and the speed dependent (complex) hard collision model (SDcHC, in which the velocity changing collision rate is characterized by a complex number) are tested using spectra of two rovibrational lines of HCl. The R(5) and R(9) lines of the fundamental band of HCl broadened by He, Ar and SF6 have been recorded with a difference-frequency laser spectrometer for total pressures ranging from 12 to 930 mbar. These lines, measured in large pressure ranges with different collision-partners provide a meaningful test of the above-mentioned line-shape models. The results confirm that non-Voigt effects are significant for HCl broadened by Ar and SF6 and mainly due to the large influence of the Dicke narrowing effect. For HCl-SF6 and HCl-Ar, especially for the R(9) line, using the β-correction together with the HT profile (and with the speed-dependent hard collision model, SDHC) significantly improves the fit residuals while it has no effect on (or tends to deteriorate) the quality of the fit for HCl-He and for the R(5) line of HCl-SF6, for which the influence of velocity changing collisions is smaller. Except for HCl-He, the SDcHC model leads to better quality of fit compared to the HT profile. The results also show that numerical correlations between refined line-shape parameters of the HT profile are important and can lead to ill-determined parameters while they are more properly determined with the SDcHC model.

Modified Complex Robert-Bonamy calculations of line shape parameters for the CO2-H2O collision system

Modified Complex Robert-Bonamy calculations were made for the CO2-H2O collision system using an intermolecular potential comprised of quadrupole-dipole, quadrupole-quadrupole, Lennard-Jones atom-atom, induction, and London dispersion terms. The initial atom-atom parameters were obtained using combination rules and the other parameters from taken from the literature. The intermolecular potential was then adjusted to give results that agree with the measurements of Sung et al. [Can. J. Phys. 87,469-484, 2009]. The final potential results (pot 46) compared with the data of Sung et al. have an average percent difference of 0.07 and a standard deviation of 1.096 %. Calculations were then made for all transitions in the 00011-00001 band with J” from 0 to 120 at 13 temperatures from 200 to 3000 K. The speed dependence of the half-width and line shift were computed for use in more advanced line shape models. The temperature dependence of the half-widths and line shifts were determined using the double power-law (DPL) model of Gamache and Vispoel [JQSRT 217, 440-452, 2018].

In vivo characterization of glycogen storage disease type III in a mouse model using glycoNOE MRI.

Glycogen storage disease type III (GSD III) is a rare inherited metabolic disease characterized by excessive accumulation of glycogen in liver, skeletal muscle, and heart. Currently, there are no widely available noninvasive methods to assess tissue glycogen levels and disease load. Here, we use glycogen nuclear Overhauser effect (glycoNOE) MRI to quantify hepatic glycogen levels in a mouse model of GSD III. Agl knockout mice (n = 13) and wild-type controls (n = 10) were scanned for liver glycogen content using glycoNOE MRI. All mice were fasted for 12 to 16 h before MRI scans. GlycoNOE signal was quantified by fitting the Z-spectrum using a four-pool Voigt lineshape model. Next, the fitted direct water saturation pool was removed and glycoNOE signal was estimated from the integral of the residual Z spectrum within -0.6 to -1.4 ppm. Glycogen concentration was also measured ex vivo using a biochemical assay. GlycoNOE MRI clearly distinguished Agl knockout mice from wild-type controls, showing a statistically significant difference in glycoNOE signals in the livers across genotypes. There was a linear correlation between glycoNOE signal and glycogen concentration determined by the biochemical assay. The obtained glycoNOE maps of mouse livers also showed higher glycogen levels in Agl knockout mice compared to wild-type mice. GlycoNOE MRI was used successfully as a noninvasive method to detect liver glycogen levels in mice, suggesting the potential of this method to be applied to assess glycogen storage diseases.

Space-resolved line shape model for sputtered atoms of finite-size targets

High-resolution emission spectroscopy provides valuable information on the physical sputtering process during plasma-wall interaction. Up to now, analyzing the observed spectral lines during sputtering did not account for the finite size of the targets. It becomes crucial if the size of the target becomes comparable with the distance the sputtered atoms travel before emitting the photons. So, for example, the generally used standard emission model based on an infinite target or the point source approximation breaks for observations using two lines of sight: parallel and perpendicular to the normal of the target. It is impossible to achieve consistent results for energy and angular distribution of sputtered atoms. The new space-resolved emission model for finite-size targets developed in this work removes this gap. It incorporates the space-velocity transformation for the distribution function and includes the finite lifetime of excited states. The model was validated using emission spectra of sputtered atoms from a polycrystalline tungsten sample bombarded by monoenergetic Ar+ with kinetic energies of 100 eV to 140 eV at normal incidence in the linear plasma device PSI-2. Using the new model enables the simultaneous fitting of the line shapes of sputtered tungsten for both observation angles. The optimization process is performed using the standard Thompson distribution by separating the energy-dependent parameter and the angular distribution.

SI-traceable validation of a laser spectrometer for balloon-borne measurements of water vapor in the upper atmosphere

Abstract. Despite its crucial role in the Earth's radiative balance, upper-air water vapor (H2O) is still lacking accurate, in situ, and continuous monitoring. Especially in the upper troposphere–lower stratosphere (UTLS), these measurements are notoriously difficult, and significant discrepancies have been reported in the past between different measuring techniques. Here, we present a laboratory assessment of a recently developed mid-IR quantum-cascade laser absorption spectrometer, called ALBATROSS, for balloon-borne measurements of H2O in the UTLS. The validation was performed using SI-traceable reference gas mixtures generated based on the permeation method and dynamic dilution. The accuracy and precision of ALBATROSS were evaluated at a wide range of pressures (30–250 mbar) and H2O amount fractions (2.5–35 ppm), representative of the atmospheric variability in H2O in the UTLS. The best agreement was achieved by implementing a quadratic speed-dependent Voigt profile (qSDVP) line shape model in the spectroscopic retrieval algorithm. The molecular parameters required by this parameterization were determined empirically using a multi-spectrum fitting approach over different pressure conditions. In the laboratory environment, ALBATROSS achieves an accuracy better than ±1.5 % with respect to the SI-traceable reference at all investigated pressures and H2O amount fractions. The measurement precision was found to be better than 30 ppb (i.e., 0.1 % at 35 ppm H2O) at 1 s resolution for all conditions. This performance, unprecedented for a balloon-borne hygrometer, demonstrates the exceptional potential of mid-IR laser absorption spectroscopy as a new reference method for in situ measurements of H2O in the UTLS.

Nuclear induction lineshape modeling via hybrid SDE and MD approach.

The temperature dependence of the nuclear free induction decay in the presence of a magnetic-field gradient was found to exhibit motional narrowing in gases upon heating, a behavior that is opposite to that observed in liquids. This has led to the revision of the theoretical framework to include a more detailed description of particle trajectories since decoherence mechanisms depend on histories. In the case of free diffusion and single components, the new model yields the correct temperature trends. The inclusion of boundaries in the current formalism is not straightforward. We present a hybrid SDE-MD (stochastic differential equation - molecular dynamics) approach whereby MD is used to compute an effective viscosity and the latter is fed to the SDE to predict the line shape. The theory is in agreement with the experiments. This two-scale approach, which bridges the gap between short (molecular collisions) and long (nuclear induction) timescales, paves the way for the modeling of complex environments with boundaries, mixtures of chemical species, and intermolecular potentials.

Analysis of Temperature-Dependent Photoluminescence Spectra in Mid-Wavelength Infrared InAs/InAsSb Type-II Superlattice

Photoluminescence (PL) is one of the commonly used methods to determine the energy gap ({E}_{mathrm{g}}) of semiconductors. In order to use it correctly, however, the shape of the PL peak must be properly analyzed; otherwise, the value of {E}_{mathrm{g}} is burdened with a large error. {E}_{mathrm{g}} is often mistakenly attributed to the PL peak position, which in type-II superlattices (T2SLs) exhibits typical “S-shaped” behavior as a function of temperature, significantly different from the Varshni model used to define the energy gap of III-V compounds. The position peak of the PL relative to the real {E}_{mathrm{g}} in T2SLs is red-shifted because of the carrier localization at low temperatures and blue-shifted because of the free carrier emission at high temperatures. To correctly determine {E}_{mathrm{g}}, the shape of the PL peak should be analyzed using the theoretical PL line shape model that takes into account both localized (below the bandgap) and free carriers (above the bandgap) emissions. This work shows that the use of such a model to analyze the shape of the PL signal gives the correct results of determining {E}_{mathrm{g}} for mid-wave infrared InAs/InAsSb T2SL, which showed a significant contribution of localized states in optical transitions and characteristic “S-shaped” PL peak behavior. This allowed us to determine the correct values of the Varshni coefficients for a given T2SL. The result also agrees with the theoretical calculations of {E}_{mathrm{g}} made using the k·p method.

Pressure and temperature dependencies of air-perturbed O[formula omitted] B-band line shapes

The air-broadened lines from the oxygen B band were measured for the first time in controlled laboratory conditions with a high signal-to-noise ratio using frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) referenced to the optical frequency comb. Spectra measured at various pressures and temperatures were analyzed with an advanced line-shape model, considering the speed-dependence of collisional broadening and shift, and the effect of velocity-changing collisions. The temperature dependence of collisional broadening and shift is determined, whereas no significant temperature dependence of speed-dependent parameters and Dicke narrowing was observed. In addition, we have demonstrated that reasonable estimation of temperature dependence for pressure broadening is possible even from measurements done in single temperature where the speed dependence of pressure broadening was determined. New spectroscopic data improve the accuracy of the air-broadened oxygen B-band spectra description by an order of magnitude.

Non-impact effects in the absorption spectra of HCl diluted in CO2, air, and He: Measurements and predictions.

Non-impact effects in the absorption spectra of HCl in various collision-partners are investigated both experimentally and theoretically. Fourier transform spectra of HCl broadened by CO2, air, and He have been recorded in the 2-0 band region at room temperature and for a wide pressure range, from 1 to up to 11.5 bars. Comparisons between measurements and calculations using Voigt profiles show strong super-Lorentzian absorptions in the troughs between successive lines in the P and R branches for HCl in CO2. A weaker effect is observed for HCl in air, while for HCl in He, Lorentzian wings are in very good agreement with measurements. In addition, the line intensities retrieved by fitting the Voigt profile on the measured spectra decrease with the density of the perturber. This perturber-density dependence decreases with the rotational quantum number. For HCl in CO2, the decrease in the retrieved line intensity can reach 2.5% per amagat for the first rotational quantum numbers. This number is about 0.8% per amagat for HCl in air, while for HCl in He, no density dependence of the retrieved line intensity is observed. Requantized classical molecular dynamics simulations have been performed for HCl-CO2 and HCl-He in order to simulate the absorption spectra for various perturber-density conditions. The density dependence of the intensities retrieved from the simulated spectra and the predicted super-Lorentzian behavior in the troughs between lines are in good agreement with experimental determinations for both HCl-CO2 and HCl-He. Our analysis shows that these effects are due to incomplete or ongoing collisions, which govern the dipole auto-correlation function at very short times. The effects of these ongoing collisions strongly depend on the details of the intermolecular potential: they are negligible for HCl-He but significant for HCl-CO2 for which a line-shape model beyond the impact approximation will be needed to correctly model the absorption spectra from the center to the far wings.

The Effect of Embedded Nanoparticles on the Phonon Spectrum of Ice: An Inelastic X-ray Scattering Study.

As a contribution to the ongoing effort toward high-frequency sound manipulation in composite materials, we use Inelastic X-ray Scattering to probe the phonon spectrum of ice, either in a pure form or with a sparse amount of nanoparticles embedded in it. The study aims at elucidating the ability of nanocolloids to condition the collective atomic vibrations of the surrounding environment. We observe that a nanoparticle concentration of about 1 % in volume is sufficient to visibly affect the phonon spectrum of the icy substrate, mainly canceling its optical modes and adding nanoparticle phonon excitations to it. We highlight this phenomenon thanks to the lineshape modeling based on a Bayesian inference, which enables us to capture the finest detail of the scattering signal. The results of this study can empower new routes toward the shaping of sound propagation in materials through the control of their structural heterogeneity.

Evaluation of spectral line mixing models and the effects on high pressure radiative heat transfer calculations

At higher pressures, the spectral lines in a gas spectrum can become more broadened and shifted due to collisional effects, leading to increased spectral line mixing. In the present study, we have reviewed different line mixing models for modeling the absorption spectra for three gases of CO2, CO, and H2O and applied these models to simulate radiative spectra for pressures within approximately 5–100 bar. The simulated data were compared with the yet-published high-pressure spectral experimental data as well as experimental data published in the literature. It has been found that the empirical “pseudo-Lorentz” line shape model considering the line mixing effects shows the best performance for modeling high-pressure gas spectra for the tested conditions, which is easy to be implemented and relatively accurate, thus is recommended for high-pressure radiative heat transfer calculations in engineering applications. Based on the selected “pseudo-Lorentz” line mixing model, we have constructed a high-pressure absorption coefficients database for CO2, CO, and H2O for pressure ranging from 1 bar to 80 bar. The newly generated database considering the spectral line mixing effects was tested for radiative heat transfer calculations, and the results were compared with the ones without considering the line mixing effects. The significance of ignoring the line mixing effects on radiative heat transfer calculations under different pressures was evaluated with one-dimensional radiative heat transfer benchmark cases. The high-pressure absorption coefficients database is available from the corresponding author upon request.

The Optical Signatures of Stochastic Processes in Many-Body Exciton Scattering.

We review our recent quantum stochastic model for spectroscopic lineshapes in the presence of a coevolving and nonstationary background population of excitations. Starting from a field theory description for interacting bosonic excitons, we derive a reduced model whereby optical excitons are coupled to an incoherent background via scattering as mediated by their screened Coulomb coupling. The Heisenberg equationsof motion for the optical excitons are then driven by an auxiliary stochastic population variable, which we take to be the solution of an Ornstein-Uhlenbeck process. Here, we present an overview of the theoretical techniques we have developed as applied to predicting coherent nonlinear spectroscopic signals. We show how direct (Coulomb) and exchange coupling to the bath give rise to distinct spectral signatures and discuss mathematical limits on inverting spectral signatures to extract the background density of states. Expected final online publication date for the Annual Review of Physical Chemistry, Volume 74 is April 2023. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Finding the bulk viscosity of air from Rayleigh-Brillouin light scattering spectra.

Spectral line shape models can successfully reproduce experimental Rayleigh-Brillouin spectra, but they need knowledge about the bulk viscosity ηb. Light scattering involves GHz frequencies, but since ηb is only documented at low frequencies, ηb is usually left as a free parameter, which is determined by a fit of the model to an experimental spectrum. The question is whether models work so well because of this freedom. Moreover, for light scattering in air, spectral models view "air" as an effective molecule. We critically evaluate the use of ηb as a fit parameter by comparing ηb obtained from fits of the Tenti S6 model to the result of Direct Simulation Monte Carlo (DSMC) for a mixture of Nitrogen and Oxygen. These simulations are used to compute light scattering spectra, which are then compared to experiments. The DSMC simulation parameters are cross-checked with a molecular dynamics simulation based on intermolecular potentials. At large values of the uniformity parameter y, y ≈ 4, where the Brillouin contribution to spectra is large, fitted ηb are 20% larger than the ones from DSMC, while the quality of the simulated spectra is comparable to that of the Tenti S6 line shape model. At smaller y, the difference between fitted and simulated ηb can be as large as 100%. We hypothesize the breakdown of the bulk viscosity concept to be the cause of this fallacy.

Open problems in liquids dynamics: The role of neutron scattering

We review recent inelastic neutron scattering experiments aimed at investigating still open issues in the microscopic dynamics of liquids. It is shown that the interpretation of experimental results is put on solid ground by the application of modern methods of analysis and lineshape modelling which ensure the fulfillment of fundamental physical properties that the spectra must obey. This last condition becomes crucial to avoid overinterpretations of the genuine information conveyed by scattering data, especially when studying weak signals in the dynamic structure factor. Moreover, we highlight the different roles that neutron data presently play compared to molecular dynamics simulations depending on the nature of the sample, including the case of quantum liquids. In particular, we show how neutron measurements remain an indispensable benchmark in assessing the present capabilities of classical and quantum simulation methods. We also mention the potential of statistical methods, such as Bayesian inference, when applied to neutron data analysis and the opportunity they provide in establishing the spectral features without arbitrary assumptions on the model lineshape.

Q-Gaussian Tsallis Line Shapes and Raman Spectral Bands

q-Gaussians are probability distributions having their origin in the framework of Tsallis statistics. A continuous real parameter q is characterizing them so that, in the range 1 < q < 3, the q-functions pass from the usual Gaussian form, for q close to 1, to that of a heavy tailed distribution, at q close to 3. The value q=2 corresponds to the Cauchy-Lorentzian distribution. This behavior of q-Gaussian functions could be interesting for a specific application, that regarding the analysis of Raman spectra, where Lorentzian and Gaussian profiles are the line shapes most used to fit the spectral bands. Therefore, we will propose q-Gaussians with the aim of comparing the resulting fit analysis with data available in literature. As it will be clear from the discussion, this is a very sensitive issue. We will also provide a detailed discussion about Voigt and pseudo-Voigt functions and their role in the line shape modeling of Raman bands. We will show a successfully comparison of these functions with q-Gaussians. The role of q-Gaussians in EPR spectroscopy (Howarth et al., 2003), where the q-Gaussian is given as the

Analysis and Modeling of Spectral Line Shapes of Collision-Induced Light Scattering of Gaseous Xenon

Collision-induced light scattering spectra of gaseous xenon at room temperature are analyzed in terms of different literature and new interatomic potentials and interaction-induced pair polarizability anisotropy and trace models. At low frequencies the spectral intensities and the associated moments are determined by both bound and free transitions.

Ion dynamics in the magnetic nozzle of a waveguide ECR thruster via laser-induced fluorescence spectroscopy

Xenon ion velocity is mapped in the magnetic nozzle (MN) of a circular waveguide electron cyclotron resonance thruster operating at 5.8 GHz by means of laser-induced fluorescence spectroscopy in the near-infrared spectral range. An array of thruster operational parameters are explored to investigate the influence on the acceleration profile and terminal ion velocity. Owing to several mechanisms which broaden the measured spectra, e.g. Paschen-Back/Zeeman effect, inference of the most probable velocity along with the axial kinetic temperature requires full lineshape modeling, especially in the near-field plume and inside the source. Ions are effectively accelerated along the MN, reaching up to 12 000 m s−1 for the lowest neutral pressure tested. A relatively large axial kinetic temperature is observed, typically in the order of 5000 K, which can be attributed to an extended ionization region that overlaps with the acceleration region.