Absorption Line Shape Research Articles

Correction of systematic low-frequency time delay errors in THz systems by absorption line shape optimization

Time-domain terahertz systems can face challenges due to systematic delay errors introduced by the employed delay mechanism, potentially leading to poor data quality. This article introduces a procedure to address these challenges by correcting low-frequency systematic errors that distort the acquired spectra and incorrectly diminish narrow absorption features. Our procedure solves an optimization problem aiming to find the corrected time-signal pairs that maximize the depth of narrow absorption features, and we highlight how the flexibility of the procedure, in principle, allows for correcting error profiles of arbitrary shape. We demonstrate the effectiveness of this approach through experiments using both simulated and experimentally recorded THz data, and the results show significant improvements in spectral accuracy. We believe this can pave the way for more reliable and precise terahertz spectroscopy measurements, enhancing its applications in various scientific and industrial fields.

Estimation of the Global Equivalence Ratio of a Swirl Combustor from a Small Number of Absorption Spectra Using Machine Learning.

A new optical diagnostic method that predicts the global fuel-air equivalence ratio of a swirl combustor using absorption spectra from only three optical paths is proposed here. Under normal operation, the global equivalence ratio and total flow rate determine the temperature and concentration fields of the combustor, which subsequently determine the absorption spectra of any combustion species. Therefore, spectra, as the fingerprint for a produced combustion field, were employed to predict the global equivalence ratio, one of the key operational parameters, in this study. Specifically, absorption spectra of water vapor at wavenumbers around 7444.36, 7185.6, and 6805.6 cm-1 measured at three different downstream locations of the combustor were used to predict the global equivalence ratio. As it is difficult to find analytical relationships between the spectra and produced combustion fields, a predictive model was a data-driven acquisition. The absorption spectra as an input were first feature-extracted through stacked convolutional autoencoders and then a dense neural network was used for regression prediction between the feature scores and the global equivalence ratio. The model could predict the equivalence ratio with an absolute error of ±0.025 with a probability of 96%, and a gradient-weighted regression activation mapping analysis revealed that the model leverages not only the peak intensities but also the variations in the shape of absorption lines for its predictions.

Collisional broadening and pressure shift coefficients for the potassium D1 and D2 transitions in oxygen and carbon dioxide at high temperatures

Collisional broadening and pressure shift parameters for the potassium resonance doublet, near 770 nm, are reported for collisions with molecular oxygen and carbon dioxide. Experiments were conducted in a reflected shock tube from 1200–2200 K and used potassium chloride (KCl) salt as the atomic potassium source. The measured absorption lineshapes were fit with Voigt profiles to infer the collisional broadening and pressure shifts. Power-law correlations were then developed to describe the pressure-normalized results as functions of temperature. Generally, the collisional broadening coefficients in oxygen agree well with theoretical predictions and are similar to those in nitrogen. Conversely, the pressure shift coefficients in oxygen differ from those in nitrogen by up to 15%. Broadening coefficients in carbon dioxide disagree with theoretical predictions by 20% or more over the range of temperatures explored in this work. These results expand the existing database of potassium lineshape coefficients, and they are expected to be useful for further development of potassium sensing diagnostics in terrestrial, Martian, and Venusian atmospheric flight studies, and in combustion systems. Other anticipated applications include interpretation of astrophysical spectroscopic observations.

Unraveling the Structure-Spectrum Relationship of Yeast Phenylalanine Transfer RNA: Insights from Theoretical Modeling of Infrared Spectroscopy.

Yeast phenylalanine tRNA (tRNAphe) is a paradigmatic model in structural biology. In this work, we combine molecular dynamics simulations and spectroscopy modeling to establish a direct link between its structure, conformational dynamics, and infrared (IR) spectra. Employing recently developed vibrational frequency maps and coupling models, we apply a mixed quantum/classical treatment of the line shape theory to simulate the IR spectra of tRNAphe in the 1600-1800 cm-1 region across its folded and unfolded conformations and under varying concentrations of Mg2+ ions. The predicted IR spectra of folded and unfolded tRNAphe are in good agreement with experimental measurements, validating our theoretical framework. We then elucidate how the characteristic L-shaped tertiary structure of the tRNA and its modulation in response to diverse chemical environments give rise to distinct IR absorption peaks and line shapes. These calculations effectively bridge IR spectroscopy experiments and atomistic molecular simulations, unraveling the molecular origins of the observed IR spectra of tRNAphe. This work presents a robust theoretical protocol for modeling the IR spectroscopy of nucleic acids, which will facilitate its application as a sensitive probe for detecting the fluctuating secondary and tertiary structures of these essential biological macromolecules.

Optical Properties of H-Bonded Heterotriangulene Supramolecular Polymers: Charge-Transfer Excitations Matter.

H-bonded N-heterotriangulene (NHT) supramolecular polymers offer a nice playground to explore the nature and dynamics of electronic excitations in low-dimensional organic nanostructures. Here, we report on a comprehensive molecular modeling of the excited-state electronic structure and optical properties of model NHT stacks, highlighting the important role of intermolecular charge-transfer (CT) excitations in shaping their optical absorption and emission lineshapes. Most importantly, we show that the coupling between the local and CT excitations, modulated by the electric fields induced by the presence of polar amide groups forming H-bonded arrays along the stacks, significantly increases the resulting hybrid exciton bandwidth. We discuss these findings in the context of the efficient transport of singlet excitons over the μm length scale reported experimentally on individual self-assembled nanofibers with molecular-scale diameter.

First-Principles Modeling of the Absorption Spectrum of Crystal Violet in Solution: The Importance of Environmentally Driven Symmetry Breaking.

Theoretical spectroscopy plays a crucial role in understanding the properties of the materials and molecules. One of the most promising methods for computing optical spectra of chromophores embedded in complex environments from the first principles is the cumulant approach, where both (generally anharmonic) vibrational degrees of freedom and environmental interactions are explicitly accounted for. In this work, we verify the capabilities of the cumulant approach in describing the effect of complex environmental interactions on linear absorption spectra by studying Crystal Violet (CV) in different solvents. The experimental absorption spectrum of CV strongly depends on the nature of the solvent, indicating strong coupling to the condensed-phase environment. We demonstrate that these changes in absorption line shape are driven by an increased splitting between absorption bands of two low-lying excited states that is caused by a breaking of the D3 symmetry of the molecule and that in polar solvents, this symmetry breaking is mainly driven by electrostatic interactions with the condensed-phase environment rather than distortion of the structure of the molecule, in contrast with conclusions reached in a number of previous studies. Our results reveal the importance of explicitly including a counterion in the calculations in nonpolar solvents due to electrostatic interactions between CV and the ion. In polar solvents, these interactions are strongly reduced due to solvent screening effects, thus minimizing the symmetry breaking. Computed spectra in methanol are found to be in reasonable agreement with the experiment, demonstrating the strengths of the outlined approach in modeling strong environmental interactions.

A time averaged semiclassical approach to IR spectroscopy.

We propose a new semiclassical approach to the calculation of molecular IR spectra. The method employs the time averaging technique of Kaledin and Miller upon symmetrization of the quantum dipole-dipole autocorrelation function. Spectra at high and low temperatures are investigated. In the first case, we are able to point out the possible presence of hot bands in the molecular absorption line shape. In the second case, we are able to reproduce accurate IR spectra as demonstrated by a calculation of the IR spectrum of the water molecule, which is within 4% of the exact intensity. Our time averaged IR spectra can be directly compared to time averaged semiclassical power spectra as shown in an application to the CO2molecule, which points out the differences between IR and power spectra and demonstrates that our new approach can identify active IR transitions correctly. Overall, the method features excellent accuracy in calculating absorption intensities and provides estimates for the frequencies of vibrations in agreement with the corresponding power spectra. In perspective, this work opens up the possibility to interface the new method with the semiclassical techniques developed for power spectra, such as the divide-and-conquer one, to get accurate IR spectra of complex and high-dimensional molecular systems.

Argon metastable density and temperature of a 94 GHz microplasma

Laser diode absorption spectroscopy is used to experimentally measure Ar(1s5) metastable density and translational gas temperature within a 94 GHz microplasma. A square two-dimensional photonic crystal (PhC) at this resonance frequency serves to ignite and sustain the plasma from 20 to 200 Torr (2.7 × 103–2.7 × 104 Pa) by using millimeter wave power from 300 to 1000 mW. Metastable density within the plasma is estimated from the absorption line shape of the laser traversing the PhC. The metastable density reaches an order of 1019 m−3 at lower pressure and decreases as pressure increases. From the Lorentzian line shape of the absorption profile at 811.53 nm, the gas temperature is extracted and found to increase from 500 K at 20 Torr to 1300 K at 200 Torr. These data are analyzed and compared with a zero-dimensional plasma model and with previous experimental plasma results at 43 GHz.

Precise Radial Velocities Using Line Bisectors

We study the properties of line bisectors in the spectrum of the Sun-as-a-star, as observed using the Integrated Sunlight Spectrometer (ISS) of the SOLIS project. Our motivation is to determine whether changes in line shape due to magnetic modulation of photospheric convection can be separated from the 9 cm s−1 Doppler reflex of the Earth’s orbit. Measuring bisectors of 21 lines over a full solar cycle, our results overwhelmingly indicate that solar magnetic activity modulates photospheric convection so as to reduce the asymmetries of line profiles in the spectrum of the Sun-as-a-star (having both C-shaped and reversed-C-shaped bisectors). However, some lines are constant or have variations in shape that are too small to measure. We inject a 9 cm s−1 radial velocity signal with a 1 yr period into the ISS spectra. Informed by a principal component analysis of the bisectors, we fit the most significant components to the bisectors of each line by linear regression, including a zero-point offset in velocity that is intended to capture the injected radial velocity signal. Averaging over lines, we are able to recover that signal to solid statistical significance in the presence of much larger changes in the line shapes. Although our work has limitations (that we discuss), we establish that changes in absorption line shapes do not in themselves prevent the detection of an Earth-like planet orbiting a Sun-like star using precise radial velocity techniques.

Real-time FPGA-based laser absorption spectroscopy using on-chip machine learning for 10 kHz intra-cycle emissions sensing towards adaptive reciprocating engines

Fast emissions sensing is needed to enable rapid optimization on-the-fly for increasingly adaptive engine architectures to improve performance over a wide range of loads and to offer fuel flexibility towards a low-carbon energy future. In this work, a real-time laser absorption spectroscopy technique is developed for 10 kHz on-line measurements of engine exhaust gas temperature and carbon monoxide. Latency due to data reduction is significantly shortened through a machine learning approach to spectral analysis and minimization of post-processing complexity for implementation on a high-bandwidth field-programmable gate array (FPGA). The data reduction method is tested on cycle-resolved laser-absorption thermochemistry measurements in reciprocating piston engine exhaust. The sensor employs a quantum cascade laser to spectrally-resolve two fundamental rovibrational absorption lines of carbon monoxide near 4.9 μm at a rate of 10 kHz. The recorded signals are passed to an FPGA to infer CO concentration and gas temperature through either a pre-trained ridge regression or artificial neural network model. Models are constructed to limit complexity with the aim of minimizing resource utilization and latency on the FPGA. Experimental data are used to evaluate the prediction accuracy of the models, with the neural network achieving RMS errors in CO mole fraction and gas temperature of 0.0390% and 15.0 K, respectively, compared to spectral fitting of the absorption lineshapes. The data reduction latencies are measured through hardware-in-the-loop demonstration, achieving a 10 kHz throughput and 25 μs latency. Computational time of the end-to-end data reduction process on the FPGA is measured at 300 ns and 600 ns for the ridge regression and neural network, respectively. The data reduction methods presented in this work expand the utility of laser absorption spectroscopy for low-latency sensors that match the timescales of combustion and increase the potential for real-time sensing and control to minimize engine exhaust emissions and maximize performance.

Numerical analysis of the Brewster-electrical duo-effect for multi-resonance tuning in THz absorber

The excitation and tuning of multiple resonances with narrow spectral width based on Brewster's effect is possible in an ultrathin dual-band terahertz absorber. The angular variation establishes a monotonic relation with the frequency of some generated resonances offering tunability. Moreover, burying a graphene ring resonator beneath the metallic ring splits the resonance for providing the triple narrow absorption windows. The electrical modulation offers the feature of independent tunability in the generated third absorption band. Thus, the frequency ratio of the upper to lower spectral absorption peak can be modulated by the electrically tunable Fermi energy of graphene. Engraving the graphene resonator also enhances the incident angle based tunability by affecting a greater number of Brewster generated resonance peaks. The narrow line shape of the triple band absorption can enable refractive index sensing and the detection of extraneous elements in localized analyte samples. The detection of imidacloprid pesticide in wheat flour is performed by the implemented sensor. The numerical analysis is done for the design and analysis of the absorber structures to report the above facts.

Quantum-Classical Protocol for Efficient Characterization of Absorption Lineshape and Fluorescence Quenching upon Aggregation: The Case of Zinc Phthalocyanine Dyes.

A quantum-classical protocol that incorporates Jahn-Teller vibronic coupling effects and cluster analysis of molecular dynamics simulations is reported, providing a tool for simulations of absorption spectra and ultrafast nonadiabatic dynamics in large molecular photosystems undergoing aggregation in solution. Employing zinc phthalocyanine dyes as target systems, we demonstrated that the proposed protocol provided fundamental information on vibronic, electronic couplings and thermal dynamical effects that mostly contribute to the absorption spectra lineshape and the fluorescence quenching processes upon dye aggregation. Decomposing the various effects arising upon dimer formation, the structure-property relations associated with their optical responses have been deciphered at atomistic resolution.

Design and evaluation of a portable frequency comb-referenced laser heterodyne radiometer

In this paper, we present the design of a laser heterodyne radiometry instrument that combines, for the first time, frequency comb calibration and a remarkably high level of portability. A design that can, therefore, be more than capable of addressing the current need for accurate ground-based greenhouse gases monitoring in urban areas and other emission hot spots. Indeed, the compact, battery-powered system allows the acquisition of atmospheric spectral characterizations, at any location, without restrictions. As its most prominent feature, the system is equipped with an electro-optic frequency comb reference that provides a set of calibration ticks from which an accurate characterization of the absorption line shape can be obtained. Besides this, the spectrometer has been designed to promptly switch between traditional operation and wavelength modulation, so the performance of future inversion models may benefit greatly by this complementary data. The system has been tested in different locations in the Madrid region (Spain), where measurements have been carried out under a wide variety of conditions. Here, a set of highly representative results is presented clearly illustrating the capabilities of the developed system.

Carbon Dioxide Concentration Estimation in Nonuniform Temperature Fields Based on Single-Pass Tunable Diode Laser Absorption Spectroscopy.

We propose a novel technique to accurately predict carbon dioxide (CO2) concentrations even in flow fields with temperature gradients based on a single laser path absorption spectrum measurement and machine learning. Concentration measurements in typical tunable diode laser absorption spectroscopy are based on a ratio of two integrated absorbances, each from a spectral line with different temperature dependence. However, the inferred concentrations can deviate significantly from the actual concentrations in the presence of temperature gradients. Furthermore, it is also difficult to find an analytical expression to compensate for the effect of nonuniform temperature profiles on concentration measurements. In this study, the entire absorption feature was considered since its shape and peak intensities vary with temperature and concentration. Specifically, a predictive model is obtained in a data-driven manner that can identify and compensate for the effect of a nonuniform temperature field on the spectrum. Despite a very detailed understanding of the CO2 absorption spectrum, it is nearly impossible to collect sufficient spectra for model acquisition by varying all temperature gradient conditions. Therefore, the model was obtained using only simulated data, much like the concept of a "digital twin". Finally, the predictive performance of the acquired model was verified using experimental data. In all test cases, the predictive performance of the model was superior to that of the two-line method. Additionally, a gradient-weighted regression activation mapping analysis confirmed that the model utilizes both the peak intensities as well as the change in the shape of absorption lines for prediction.

Extracting accurate infrared lineshapes from weak vibrational probes at low concentrations

Fourier-transform infrared (FTIR) spectroscopy using vibrational probes is an ideal tool to detect changes in structure and local environments within biological molecules. However, challenges arise when dealing with weak infrared probes, such as thiocyanates, due to their inherent low signal strengths and overlap with solvent bands. In this protocol we demonstrate:•A streamlined approach for the precise extraction of weak infrared absorption lineshapes from a strong solvent background.•A protocol combining a spectral filter, background modeling, and subtraction.•Our methodology successfully extracts the CN stretching mode peak from methyl thiocyanate at remarkably low concentrations (0.25 mM) in water, previously a challenge for FTIR spectroscopy.This approach offers valuable insights and tools for more accurate FTIR measurements using weak vibrational probes. This enhanced precision can potentially enable new approaches to enhance our understanding of protein structure and dynamics in solution.

High band-width mid-infrared frequency-modulated Faraday rotation spectrometer for time resolved measurement of the OH radical.

We present a novel mid-infrared frequency-modulated Faraday rotation spectrometer (FM-FRS) for highly sensitive and high bandwidth detection of OH radicals in a photolysis reactor. High frequency modulation (up to 150 MHz) of the probe laser using an electro-optical modulator (EOM) was used to produce a modulation sideband on the laser output. An axial magnetic field was applied to the multi-pass Herriott cell, causing the linearly polarized light to undergo Faraday rotation. OH radicals were generated in the cell by photolyzing a mixture of ozone (O3) and water (H2O) with a UV laser pulse. The detection limit of OH reaches 6.8 × 108 molecule/cm3 (1σ, 0.2 ms) after 3 and falling to 8.0 × 107 molecule/cm3 after 100 event integrations. Relying on HITRAN absorption cross section and line shape data, this corresponds to minimum detectable fractional absorption (Amin) of 1.9 × 10-5 and 2.2 × 10-6, respectively. A higher signal-to-noise ratio and better long-term stability was achieved than with conventional FMS because the approach was immune to interference from diamagnetic species and residual amplitude modulation noise. To our knowledge, this work reports the first detection of OH in a photolysis reactor by FM-FRS in the mid-infrared region, a technique that will provide a new and alternative spectroscopic approach for the kinetic study of OH and other intermediate radicals.

The CARMENES search for exoplanets around M dwarfs

Context. Radial velocities (RVs) measured from high-resolution stellar spectra are routinely used to detect and characterise orbiting exoplanet companions. The different lines present in stellar spectra are created by several species, which are non-uniformly affected by stellar variability features such as spots or faculae. Stellar variability distorts the shape of the spectral absorption lines from which precise RVs are measured, posing one of the main problems in the study of exoplanets. Aims. In this work we aim to study how the spectral lines present in M dwarfs are independently impacted by stellar activity. Methods. We used CARMENES optical spectra of six active early- and mid-type M dwarfs to compute line-by-line RVs and study their correlation with several well-studied proxies of stellar activity. Results. We are able to classify spectral lines based on their sensitivity to activity in five M dwarfs displaying high levels of stellar activity. We further used this line classification to compute RVs with activity-sensitive lines and less sensitive lines, enhancing or mitigating stellar activity effects in the RV time series. For specific sets of the least activity-sensitive lines, the RV scatter decreases by ~2 to 5 times the initial one, depending on the star. Finally, we compare these lines in the different stars analysed, finding the sensitivity to activity to vary from star to star. Conclusions. Despite the high density of lines and blends present in M dwarf stellar spectra, we find that a line-by-line approach is able to deliver precise RVs. Line-by-line RVs are also sensitive to stellar activity effects, and they allow for an accurate selection of activity-insensitive lines to mitigate activity effects in RV. However, we find stellar activity effects to vary in the same insensitive lines from star to star.

Search for ferromagnetism in Mn-doped lead halide perovskites

Lead halide perovskites are new key materials in various application areas such as high efficiency photovoltaics, lighting, and photodetectors. Doping with Mn, which is known to enhance the stability, has recently been reported to lead to ferromagnetism below 25 K in methylammonium lead iodide (MAPbI3) mediated by superexchange. Two most recent reports confirm ferromagnetism up to room temperature but mediated by double exchange between Mn2+ and Mn3+ ions. Here we investigate a wide concentration range of MAMnxPb1−xI3 and Mn-doped triple-cation thin films by soft X-ray absorption, X-ray magnetic circular dichroism, and quantum interference device magnetometry. The X-ray absorption lineshape shows clearly an almost pure Mn2+ configuration, confirmed by a sum-rule analysis of the dichroism spectra. A remanent magnetization is not observed down to 2 K. Curie-Weiss fits to the magnetization yield negative Curie temperatures. All data show consistently that significant double exchange and ferromagnetism do not occur. Our results show that Mn is not suitable for creating ferromagnetism in lead halide perovskites.

Narrow homogeneous linewidths and slow cooling dynamics across infrared intra-band transitions in n-doped HgSe colloidal quantum dots.

Intra-band transitions in colloidal quantum dots (QDs) are promising for opto-electronic applications in the mid-IR spectral region. However, such intra-band transitions are typically very broad and spectrally overlapping, making the study of individual excited states and their ultrafast dynamics very challenging. Here, we present the first full spectrum two-dimensional continuum infrared (2D CIR) spectroscopy study of intrinsically n-doped HgSe QDs, which exhibit mid-infrared intra-band transitions in their ground state. The obtained 2D CIR spectra reveal that underneath the broad absorption line shape of ∼500cm-1, the transitions exhibit surprisingly narrow intrinsic linewidths with a homogeneous broadening of 175-250cm-1. Furthermore, the 2D IR spectra are remarkably invariant, with no signof spectral diffusion dynamics at waiting times up to 50ps. Accordingly, we attribute the large static inhomogeneous broadening to the distribution of size and doping level of the QDs. In addition, the two higher-lying P-states of the QDs can be clearly identified in the 2D IR spectra along the diagonal with a cross-peak. However, there is no indication of cross-peak dynamics indicating that, despite the strong spin-orbit coupling in HgSe, transitions between the P-states must be longer than our maximum waiting time of 50ps. This study illustrates a new frontier of 2D IR spectroscopy enabling the study of intra-band carrier dynamics in nanocrystalline materials across the entire mid-infrared spectrum.

Collision-induced absorption spectra (CIA) for monatomic gas mixtures of Helium-Xenon

The lineshapes of collision-induced absorption (CIA) at room temperature are computed quantum mechanically for gaseous binary mixtures of helium with xenon using theoretical induced dipole moment and interatomic potentials. Empirical and literature models of the induced dipole moments which reproduce the experimental spectra and the first few spectral moments are given. Good agreement between the computed and experimental lineshapes of absorption is obtained when the potential parameters which are fitted well to the vibrational energy levels, thermophysical and transport properties are used.