Lineshape Profile Research Articles

Interplay between electromagnetically induced transparency (EIT), absorption (EIA), and Autler-Townes (AT) splitting in an N-type atomic system: experiment and theory

In this article we have shown that the atomic states can be engineered by tunning the coupling Rabi frequency for a system with $\mathcal{N}$-type configuration. Electromagnetically induced transparency (EIT), Electromagnetically induced absorption (EIA) and Autler-Townes (AT) splitting has been observed experimentally in a four level $\mathcal{N}$-type atomic vapor of $^{85}Rb$ atoms in the hyperfine levels of $D_2$ transition. It has been shown that the response of the atomic medium can be tunned from highly transparent to highly absorptive in our case. The evolution of the atomic states from the dark state |D> to the non-coupled state |NC> has been studied with the partial dressed state approach which makes the backbone of the modification of the atomic response. In addition, transient solutions in the time domain and steady state solution in the frequency domain has been studied. The population dynamics and the coherence contribution in each case has been analyzed by the time dependent solutions. The experimentally observed steady line-shape profiles has been supported by the steady state solution of optical-Bloch equations considering the Maxwell Boltzmann velocity distributions of the atoms. It has been observed that the crossover between the EIT and the AT splitting has been replaced by the interference contribution of the EIA in this $\mathcal{N}$-type system.

A new line-shape asymmetry model for wavelength modulation spectroscopy in gaseous flows

Abstract This communication reports technical notes on the development and application of an automated line-shape fitting procedure for wavelength modulation spectroscopy (WMS). Near-infrared transitions of carbon dioxide (CO2) around 1573 nm were measured in vertical cold (nonreacting) flow of CO2 at atmospheric pressure using WMS with demodulation at second harmonic frequency. Semi-empirical model based on the set of so-called Gabor functions was developed and parameters of Lorentzian line-shape profile and its asymmetry resulting from simultaneous frequency and amplitude response of the current-modulated semiconductor laser were determined. Nonlinear least-square fitting procedure employing differential evolution algorithm was successfully utilized for performing this task. Line-shape fitting procedure enabling efficient signal de-noising and background subtraction of wavelength modulation spectra was implemented into an open-source code.

Speed-dependent Voigt lineshape parameter database from dual frequency comb measurements at temperatures up to 1305 K. Part II: Argon-broadened H2O absorption, 6801–7188 cm−1

We report argon-broadened water vapor transition parameters and their temperature dependence based on measured spectra spanning 6801–7188 cm−1 from a broad-bandwidth, high-resolution dual frequency comb spectrometer. The 25 collected spectra of 2% water vapor in argon ranged from 296 K to 1305 K with total pressure spanning 100 Torr to 600 Torr. A multispectrum fitting routine was used in conjunction with a quadratic speed-dependent Voigt profile to extract broadening and shift parameters, and a power-law temperature-dependence exponent for both. The measurements represent the first broad bandwidth, argon-broadened water vapor absorption study, and are an important step toward a foreign-gas-perturbed, high-temperature database developed using advanced lineshape profiles.

Speed-dependent Voigt lineshape parameter database from dual frequency comb measurements up to 1305 K. Part I: Pure H2O absorption, 6801–7188 cm−1

We measure speed-dependent Voigt lineshape parameters with temperature-dependence exponents for several hundred spectroscopic features of pure water spanning 6801–7188 cm−1. The parameters are extracted from broad bandwidth, high-resolution dual frequency comb absorption spectra with multispectrum fitting techniques. The data encompass 25 spectra ranging from 296 K to 1305 K and 1 to 17 Torr of pure water vapor. We present the extracted parameters, compare them to published data, and present speed-dependence, self-shift, and self-broadening temperature-dependent parameters for the first time. Lineshape data is extracted using a quadratic speed-dependent Voigt profile and a single self-broadening power law temperature-dependence exponent over the entire temperature range. The results represent an important step toward a new high-temperature database using advanced lineshape profiles.

Rovibrational line-shape parameters for H2 in He and new H2-He potential energy surface

We report a new H2-He potential energy surface that, with respect to the previous one [Bakr et al.(2013)], covers much larger range of H2 stretching and exhibits more accurate asymptotic behavior for large separations between H2 and He. Close-coupling calculations performed on this improved potential energy surface allow us to provide line shape parameters for H2 between 5 and 2000 K for Raman isotropic Q lines and anisotropic Q lines (or electric quadrupole lines) and for vibrational bands from the ground up to v=5 and rotational quantum numbers up to j=5. The parameters provided include the usual pressure -broadening and -shifting coefficients as well as the real and imaginary part of Dicke contribution to the Hess profile. The latter parameters can be readily implemented in other line-shape profiles like the most recent one of Hartmann and Tran.

Coupled-square-well model and Fano-phase correspondence

This paper investigates the Fano-Feshbach resonance with a two-channel coupled-square-well model in both the frequency and time domains. This systems is shown to exhibit Fano lineshape profiles in the energy absorption spectrum. The associated time-dependent dipole response has a phase shift that has recently been understood to be related to the Fano lineshape asymmetric $q$ parameter by $\phi=2arg(q-i)$. The present study demonstrates that the phase-$q$ correspondence is general for any Fano resonance in the weak coupling regime, independent of the transition mechanism.

Measurements and modeling of 16O12C17O spectroscopic parameters at 2 µm

The lack of spectroscopic measurements for rare CO2 isotopologues was the main motivation of this work. In our present study we report line intensity measurements for 16O12C17O made with a high resolution Fourier transform spectrometer (Bruker IFS-125HR) and a 21 m path cryogenic Herriott cell at Jet Propulsion Laboratory. For this, a 17O-enriched CO2 gas sample was used, which comes as a mixture of primary and several minor CO2 isotopologues. The mole fraction of the 16O12C17O isotopologue in the mixture was determined to be 0.3991 by mass spectrometry from a Stable Isotope Ratio Mass Spectrometer (SIRMS) under stochastic distribution assumption at thermal equilibrium. Since the collisional narrowing effect was observed, the Rautian molecular line shape profile was systematically adopted instead of the Voigt profile. Absolute line positions were also investigated by performing a wavenumber calibration based on CO, HCl and a few well-known 16O12C16O transitions. Finally, around 1000 transitions were studied between 4604 and 5126cm−1 involving 15 bands of the 16O12C17O isotopologue. All the measured line intensities were renormalized to be the values for 100% pure isotopologue sample. Transition dipole moments and Herman-Wallis factors were derived enabling a global comparison with theoretical calculations and predictions for the 15 bands of the 16O12C17O isotopologue. For the measured line positions, the absolute accuracy is around 2×10−4cm−1. The accuracies of retrieved line intensities are 2 – 5% for five cold and two hot bands, and 6–30% for eight other weaker hot bands. Results from this work were in a good agreement with HITRAN 2012 for positions, but showed rather significant discrepancies for line intensities. An extensive line list was generated from new experimental measurements in order to improve and validate spectroscopic knowledge of 12C16O17O isotopologue in support of atmospheric remote sensing for the Earth (e.g., OCO-2 mission), Mars and Venus.

Parameters of broadening of water molecule absorption lines by argon derived using different line profile models

The water vapor absorption spectrum was measured in the spectral region 6700–7650 cm–1 with argon as a buffer gas. The room-temperature spectrum was measured using a Bruker IFS 125-HR Fourier Transform Spectrometer with high signal-to-noise ratio, with a spectral resolution of 0.01 cm–1, at argon pressures from 0 to 0.9 atm. The H2O absorption spectral line parameters are derived by fitting two line shape profiles (Voigt and speed-dependent Voigt) to the experimental spectrum. It is shown that the use of speed-dependent Voigt profile provides the best agreement with experimental data.

13C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14-Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D (13)C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically (13)C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14-Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m c14 and m c38). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for (13)C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m c38 isomerization, the (1)H-(13)C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

Towards a standard for the dynamic measurement of pressure based on laser absorption spectroscopy

We describe an approach for creating a standard for the dynamic measurement of pressure based on the measurement of fundamental quantum properties of molecular systems. From the linewidth and intensities of ro-vibrational transitions we plan on making an accurate determination of pressure and temperature. The goal is to achieve an absolute uncertainty for time-varying pressure of 5% with a measurement rate of 100 kHz, which will in the future serve as a method for the traceable calibration of pressure sensors used in transient processes. To illustrate this concept we have used wavelength modulation spectroscopy (WMS), due to inherent advantages over direct absorption spectroscopy, to perform rapid measurements of carbon dioxide in order to determine the pressure. The system records the full lineshape profile of a single ro-vibrational transition of CO2 at a repetition rate of 4 kHz and with a systematic measurement uncertainty of 12% for the linewidth measurement. A series of pressures were measured at a rate of 400 Hz (10 averages) and from these measurements the linewidth was determined with a relative uncertainty of about 0.5% on average. The pressures measured using WMS have an average difference of 0.6% from the absolute pressure measured with a capacitance diaphragm sensor.

HITRANonline: An online interface and the flexible representation of spectroscopic data in the HITRAN database

We describe a new, online interface to the HITRAN database that overcomes the many limitations of the existing, 160-character fixed-width, text based format (the “.par” files mostly distributed through an FTP site until now). The interface, called HITRANonline, accesses a relational database [JQSRT 2013:130, 57-61] in which the spectroscopic data are stored in a flexible, extensible and structured format. This allows an arbitrary number of different parameters for each transition to be stored so that HITRAN can represent, for example, non-Voigt line shape profiles as well as parameters representing broadening by species other than “air” and “self”.The online interface provides many ways of visualizing data as part of querying the database and allows users to create and save their own output formats to suit their own needs. A bibliography file produced with each data file provides citations and notes to the original data sources to make it easier for users to credit data providers. Once registered with the HITRANonline service, users also have (private) access to thier own search history which summarizes and can repeat queries.

Temperature dependence of peptide carboxylic group IR spectra in the amide I′ region at neutral and acidic pH

Analysis of the temperature-dependent amide I′ bands of peptides and proteins can be complicated by their overlap with other IR bands, particularly those of carboxylic groups of amino acid side-chains and the C-terminus. Previously, we reported IR spectra of charged carboxylic side-chains in Asp and Glu amino acids, and C-terminal groups of several amino acids and dipeptides at neutral pH. To complement these results, here we investigate the IR absorptions of Asp and Glu side-chains in capped amino acids (AcAspNMe and AcGluNMe), at both neutral and acidic pH. Spectra of protonated (acidic pH) C-terminal group absorptions are also investigated, using three dipeptides (AlaGly GlyAla and GlyGly) as model compounds. Sets of temperature-dependent experimental IR spectra were analyzed using pseudo-Voigt lineshape profiles. We find that the temperature-dependent behavior of the IR bands of deprotonated (neutral pH) side-chains in AcAspNMe and AcGluNMe dipeptides are generally similar to those reported previously for Asp and Glu. Protonated carboxylic group (acidic pH) IR bands behave uniformly with respect to temperature, showing very similar magnitude frequency shifts and intensity changes. Implications for analyses of amide I′ bands of peptides and proteins are discussed.

Perturbative multireference configuration interaction (CI-MRPT2) calculations in a focused dynamical approach: a computational study of solvatochromism in pyrimidine.

We have investigated solvatochromic effects over a solvent series of increasing polarity on the prototype molecule pyrimidine as a solute species. The line shape profiles, obtained by a time-dependent approach based on quantum mechanical calculations performed over frames sampled from classical molecular dynamics trajectories, were directly compared to the available experimental bands. The multireference configuration interaction second-order perturbation (CI-MRPT2) calculations are in quantitative agreement with the experiment. The results also confirm how nonprotic solvents can be confidently modeled by continuous solvation models as the polarizable continuum model, whereas protic solvents, as water, require the inclusion of explicit solvent molecules to account for the effects of hydrogen bonds.

Observation of Lorentzian lineshapes in the room temperature optical spectra of strongly coupled Jaggregate/metal hybrid nanostructures by linear two-dimensional optical spectroscopy

We analyze the linear optical reflectivity spectra of a prototypical, strongly coupled metal/molecular hybrid nanostructure by means of a new experimental approach, linear two-dimensional optical spectroscopy. White-light, broadband spectral interferometry is used to measure amplitude and spectral phase of the sample reflectivity or transmission with high precision and to reconstruct the time structure of the electric field emitted by the sample upon impulsive excitation. A numerical analysis of this time-domain signal provides a two-dimensional representation of the coherent optical response of the sample as a function of excitation and detection frequency. The approach is used to study a nanostructure formed by depositing a thin J-aggregated dye layer on a gold grating. In this structure, strong coupling between excitons and surface plasmon polaritons results in the formation of hybrid polariton modes. In the strong coupling regime, Lorentzian lineshape profiles of different polariton modes are observed at room temperature. This is taken as an indication that the investigated strongly coupled polariton excitations are predominantly homogeneously broadened at room temperature. This new approach presents a versatile, simple and highly precise addition to nonlinear optical spectroscopic techniques for the analysis of line broadening phenomena.

Fano resonance in anodic aluminum oxide based photonic crystals

Anodic aluminum oxide based photonic crystals with periodic porous structure have been prepared using voltage compensation method. The as-prepared sample showed an ultra-narrow photonic bandgap. Asymmetric line-shape profiles of the photonic bandgaps have been observed, which is attributed to Fano resonance between the photonic bandgap state of photonic crystal and continuum scattering state of porous structure. And the exhibited Fano resonance shows more clearly when the sample is saturated ethanol gas than air-filled. Further theoretical analysis by transfer matrix method verified these results. These findings provide a better understanding on the nature of photonic bandgaps of photonic crystals made up of porous materials, in which the porous structures not only exist as layers of effective-refractive-index material providing Bragg scattering, but also provide a continuum light scattering state to interact with Bragg scattering state to show an asymmetric line-shape profile.

Automated Quantitative Spectroscopic Analysis Combining Background Subtraction, Cosmic Ray Removal, and Peak Fitting

An integrated concept for post-acquisition spectrum analysis was developed for in-line (real-time) and off-line applications that preserves absolute spectral quantification; after the initializing parameter setup, only minimal user intervention is required. This spectral evaluation suite is composed of a sequence of tasks specifically addressing cosmic ray removal, background subtraction, and peak analysis and fitting, together with the treatment of two-dimensional charge-coupled device array data. One may use any of the individual steps on their own, or may exclude steps from the chain if so desired. For the background treatment, the canonical rolling-circle filter (RCF) algorithm was adopted, but it was coupled with a Savitzky-Golay filtering step on the locus-array generated from a single RCF pass. This novel only-two-parameter procedure vastly improves on the RCF's deficiency to overestimate the baseline level in spectra with broad peak features. The peak analysis routine developed here is an only-two-parameter (amplitude and position) fitting algorithm that relies on numerical line shape profiles rather than on analytical functions. The overall analysis chain was programmed in National Instrument's LabVIEW; this software allows for easy incorporation of this spectrum analysis suite into any LabVIEW-managed instrument control, data-acquisition environment, or both. The strength of the individual tasks and the integrated program sequence are demonstrated for the analysis of a wide range of (although not necessarily limited to) Raman spectra of varying complexity and exhibiting nonanalytical line profiles. In comparison to other analysis algorithms and functions, our new approach for background subtraction, peak analysis, and fitting returned vastly improved quantitative results, even for "hidden" details in the spectra, in particular, for nonanalytical line profiles. All software is available for download.

Feature extraction for gas photoacoustic spectroscopy and content inverse based on overcomplete ICA bases

In near-infrared band, macro representations of rovibrational-transition absorptions of some low molecule mass gases are “spiky” transient lines. The pressure broadening at ambient temperature and pressure make lineshape profiles at adjacent wavelength produce mutual projection or superposition, and it makes the “spiky” absorption features just be hidden in observable spectra. A blind source separation (BSS) model can extract features which hide within sampled spectra data, if a mixed gas phase photoacoustic signal is regarded as the weighted sum of feature absorptions by the spacing between adjacent feature wavelengths. A BSS model based on overcomplete ICA basis is proposed, and a weight truncation equation for transforming ICA bases based on the five-point sampling method is created so that a FastICA algorithm based on a negentropy approximation can be used to extract feature components. The resulting validity test using data from a real-time experiment of gas detection showed that the method detection limit can be improved from 16ppb to 10ppb with improved accuracy and signal-to-noise ratio.

Extended line positions, intensities, empirical lower state energies and quantum assignments of NH3 from 6300 to 7000 cm−1

Nearly 4800 features of ammonia between 6300 and 7000cm−1 with intensities ≥4×10−24cm−1/(molecule·cm−2) at 296K were measured using 16 pure NH3 spectra recorded at various temperatures (296–185K) with the McMath–Pierce Fourier Transform Spectrometer at Kitt Peak National Observatory, AZ. The line positions and intensities were retrieved by fitting individual spectra based on a Voigt line shape profile and then averaging the values to form the experimental linelist. The integrated intensity of the region was 4.68×10−19cm−1/(molecule·cm−2) at 296K. Empirical lower state energies were also estimated for 3567 absorption line features using line intensities retrieved from 10 spectra recorded at gas temperature between 185 and 233K. Finally, using Ground State Combination Differences (GSCDs) and the empirical lower state energy estimates, the quantum assignments were determined for 1096 transitions in the room temperature linelist, along with empirical upper state energies for 434 levels. The assignments correspond to seven vibrational states, as confirmed from recent ab initio calculations. The resulting composite database of 14NH3 line parameters will provide experimental constraints to ab initio calculations and support remote sensing of gaseous bodies including the atmospheres of Earth, (exo)planets, brown dwarfs, and other astrophysical environments.

A HIGH-RESOLUTION PHOTOIONIZATION AND PHOTOELECTRON STUDY OF58Ni USING A VACUUM ULTRAVIOLET LASER

In order to provide high-resolution spectroscopic data of nickel (58Ni) and its cation (58Ni+) for the assignment of vacuum ultraviolet (VUV) stellar spectra, we have obtained the photoionization efficiency (PIE) spectra of 58Ni by using a supersonically cooled laser ablation transition-metal beam source and a broadly tunable VUV laser in the range of 61,100-73,600 cm–1, covering the photoionization transitions: Ni+ (3d 9 2 D) ← Ni (3d 84s 2 3 D), Ni+(3d 9 2 D) ← Ni(3d 84s 2 3 F), and Ni+ (3d 84s 4 F) ← Ni(3d 84s 2 3 F). We have also measured the VUV laser pulsed-field-ionization-photoelectron (PFI-PE) spectra of 58Ni in these regions. The VUV-PFI-PE measurement has allowed the determination of a precise value of 61,619.89 ± 0.8 cm–1 (7.6399 ± 0.0001 eV) for the ionization energy (IE) of 58Ni. Due to the narrow VUV laser optical bandwidth of 0.4 cm–1 used in the present study, many complex autoionizing resonances exhibiting Fano line shape profiles are resolved in the PIE spectra. Four autoionizing Rydberg series originating from two-electron and one-electron excitations from the Ni(3d 84s 2 3 F 4) ground state to converge to the respective Ni+(2 D 3/2) and Ni+(4 FJ ) (J = 9/2, 7/2, and 5/2) ion states are identified. The Rydberg analysis, along with VUV-PFI-PE measurements, has yielded highly precise IE values for the formation of these excited ionic states from the Ni(3d 84s 2 3 F 4) ground state. The IE values, relative photoionization cross sections, and autoionizing Rydberg resonances observed in the present study are relevant to astrophysics by enhancing the atomic database of iron group transition metal atoms and for understanding the Ni and Ni+ contribution to the VUV opacity in the solar atmosphere.

Absorption spectra of natural pigments as sensitizers in solar cells by TD-DFT and MRPT2: protonated cyanidin

The study of molecular species suitable as sensitizers in solar cells involves the understanding of their visible absorption spectrum. In this article we present a detailed theoretical study of the visible band which has been observed for cyanidin in acid solution. We performed accurate DFT and MRPT2 calculations on the protonated cyanidin in vacuo and in solution, where we have also computed the lineshape profile by including the effects of nuclear degrees of freedom in the harmonic approximation.