Absorption Line Shape Research Articles

Simulation of attosecond transient soft x-ray absorption in solids using generalized Kohn–Sham real-time time-dependent density functional theory

Time-dependent density functional theory (TDDFT) simulations of transient core-level spectroscopies require a balanced treatment of both valence- and core-electron excitations. To this end, tuned range-separated hybrid exchange–correlation functionals within the generalized Kohn–Sham scheme offer a computationally efficient means of simultaneously improving the accuracy of valence and core excitation energies in TDDFT by mitigating delocalization errors across multiple length-scales. In this work range-separated hybrid functionals are employed in conjunction with the velocity-gauge formulation of real-time TDDFT to simulate static as well as transient soft x-ray near-edge absorption spectra in a prototypical solid-state system, monolayer hexagonal boron nitride, where excitonic effects are important. In the static case, computed soft x-ray absorption edge energies and line shapes are seen to be in good agreement with experiment. Following laser excitation by a pump pulse, soft x-ray probe spectra are shown to exhibit characteristic features of population induced bleaching and transient energy shifts of exciton peaks. The methods outlined in this work therefore illustrate a practical means for simulating attosecond time-resolved core-level spectra in solids within a TDDFT framework.

Optimizing the Multimode Brownian Oscillator Model for the Optical Response of Carotenoids in Solution by Fine Tuning of Differential Evolution

During last twenty years, the Differential evolution algorithm (DE) has proved to be one of the powerful methods to solve minimization problems for multidimensional functions. Being a member of the family of evolutionary optimization algorithms, its main principle is based upon the concepts of natural selection and mutation. In this study, we test the potential of DE to find a proper set of parameters for the multimode Brownian oscillator model, which was then used to simulate absorption lineshapes of carotenoid molecules in solution: spheroidene and spheroidenone. This theory assumes that the correlation function of a particular electronic state of the carotenoid is calculated using the semiclassical spectral density function. Considering our previous studies on photosynthetic pigments, we employed several DE strategies to do fitting of the carotenoid experimental spectra. We found that simulated absorption spectra are very sensitive to several parameters that characterize carotenoid vibronic modes, namely, Huang–Rhys factors. Fine tuning of DE crossover parameter (Cr) and the scaling factor (F) provided acceptable convergence of the algorithm. It appears that to get good convergence of DE, a certain spectral range of carotenoid absorption from 400 to 600 nm must be chosen. This fact can be explained by the limitations of the applied theory, which simply does not predict properly the carotenoid absorption at higher frequencies.

Multispectrum rotational states distribution thermometry: application to the 3ν1 + ν3 band of carbon dioxide

In this paper we propose multispectrum rotational states distribution thermometry as an optical method for primary thermometry. It relies on a global fitting of multiple absorption lines of the same band at different pressures. The approach allows leveraging both the temperature-dependent Doppler width and the temperature-dependent distribution of line intensities across the ro-vibrational band. We provide a proof-of-principle demonstration of the approach on the 3ν1 + ν3 band of CO2, for which several accurate line-strength models of both theoretical and experimental origin are available for the global fitting. Our experimental conditions do not allow to test the methodology beyond a combined uncertainty of 530 ppm, but the comparative analysis between different line-strength models shows promise to reduce the error budget to few tens of ppm. As compared to Doppler-broadening thermometry, the approach is advantageous to mitigate systematic errors induced by a wrong modelling of absorption line-shapes and to reduce, for a given experimental dataset, the statistical uncertainty by a factor of 2. When applied in a reverse way, i.e. using a gas of known temperature, the approach becomes a stringent testbed for the accuracy of the adopted line-strength model.

MHz laser absorption spectroscopy via diplexed RF modulation for pressure, temperature, and species in rotating detonation rocket flows

A mid-infrared laser absorption sensing method has been developed to quantify gas properties (temperature, pressure, and species density) at MHz measurement rates, with application to annular rotating detonation rocket flows. Bias-tee circuitry is integrated with distributed feedback quantum cascade and interband cascade lasers in the $$4{-}5~\mu \hbox {m}$$ range enabling diplexed radio frequency (RF) wavelength modulation on the order of several MHz while yielding sufficient scan depth to capture multiple rovibrational transitions in the fundamental vibrational bands of $${\text {CO}}$$ and $${\text {CO}}_{2}$$ . Sub-microsecond spectrally-resolved $${\text {CO}}$$ absorption lineshapes provide for inference of temperature and species from a two-line area ratio and pressure from collision line-width. $${\text {CO}}_{2}$$ column density is inferred from peak-to-valley differential absorption at the bandhead near $$4.19~\mu \hbox {m}$$ . A field demonstration on a methane-oxygen rotating detonation rocket engine was performed utilizing an in situ single-ended retro-reflection optical configuration aligned at the exhaust plane. The target gas properties are temporally-resolved at up to 3 MHz across rotating detonations with up to 20 kHz cycle frequency.

Effects of temperature and pressure on OH laser-induced fluorescence exciting A–X (1,0) transition at high pressures**Project supported by the National Natural Science Foundation of China (Grant Nos. 51976233 and 91641118).

The effects of temperature and pressure on laser-induced fluorescence (LIF) of OH are numerically studied under the excitation of A–X (1,0) transition at high pressures. A detailed theoretical analysis is carried out to reveal the physical processes of LIF. It is shown that high pressure LIF measurements get greatly complicated by the variations of pressure- and temperature-dependent parameters, such as Boltzmann fraction, absorption lineshape broadening, central-frequency shifting, and collisional quenching. Operations at high pressures require a careful choice of an excitation line, and the Q1(8) line in the A–X (1,0) band of OH is selected due to its minimum temperature dependence through the calculation of Boltzmann fraction. The absorption spectra of OH become much broader as pressure increases, leading to a smaller overlap integral and thus smaller excitation efficiency. The central-frequency shifting cannot be omitted at high pressures, and should be taken into account when setting the excitation frequency. The fluorescence yield is estimated based on the LASKIN calculation. Finally, OH-LIF measurements were conducted on flat stoichiometric CH4/air flames at high pressures. And both the numerical and experimental results illustrate that the pressure dependence of fluorescence yield is dominated, and the fluorescence yield is approximately inversely proportional to pressure. These results illustrate the physical processes of OH-LIF and provide useful guidelines for high-pressure application of OH-LIF.

Doppler narrowing of EIT linewidth in closed-loop systems

We theoretically investigate a five-level closed-loop M-type atomic system and a three-level closed-loop $$\Lambda $$ -system in hot atomic vapour. In contrast to closed-loop $$\Lambda $$ -system, two unpopulated ground states of the M-system are coupled by a microwave field. We find that thermal averaging in the M-system causes many interesting modification of probe absorption lineshape including narrowing, splitting and absorption enhancement. In M-system, the linewidth of probe absorption after thermal averaging becomes remarkably narrow (100 times smaller) with respect to the linewidth of stationary atoms. On the contrary, the closed-loop $$\Lambda $$ -system generates only 1.6 times smaller linewidth in thermal vapour. The absence of population transfer through the microwave field leads to this significant narrowing effect in the M-system which is unachievable in closed-loop $$\Lambda $$ -systems. Hence, M-system has potential application in high-resolution spectroscopy, generation of ultra slow light, phase-dependent optical switching, and in microwave electro- and magnetometry.

CLS Next Gen: Accurate Frequency-Frequency Correlation Functions from Center Line Slope Analysis of 2D Correlation Spectra Using Artificial Neural Networks.

The center line slope (CLS) observable has become a popular method for characterizing spectral diffusion dynamics in two-dimensional (2D) correlation spectroscopy because of its ease of implementation, robustness, and clear theoretical relationship to the frequency-frequency correlation function (FFCF). The FFCF relates the frequency fluctuations of an ensemble of chromophores to coupled bath modes of the chemical system and is used for comparison to molecular dynamics simulations and for calculating 2D spectra. While in the appropriate limits, the CLS can be shown to be the normalized FFCF, from which the full FFCF can be obtained, in practice the assumptions that relate the CLS to the normalized FFCF are frequently violated. These violations are due to the presence of homogeneous broadening and motional narrowing. The generalized problem of relating the CLS to the FFCF is reanalyzed by introducing a new set of dimensionless parameters for both the CLS and FFCF. A large data set was generated of CLS parameters derived from numerically modeled 2D line shapes with known FFCF parameters. This data set was used to train feedforward artificial neural networks that act as functions, which take the CLS parameters as inputs and return FFCF parameters. These neural networks were deployed in an algorithm that is able to quickly and accurately determine FFCF parameters from experimental CLS parameters and the fwhm of the absorption line shape. The method and necessary inputs to accurately obtain the FFCF from the CLS are presented.

Mirror symmetric broadband homodecoupled perfect echo spectroscopy

A new experiment for recording phase sensitive ω1-broadband homodecoupled TOCSY spectra is presented. The method is an extension of the already existing perfect echo (PE) filter, proposed to sample t1 chemical shift under sustained homodecoupling. The modification is made by attaching a time reversed perfect echo filter to a regular perfect echo scheme. Thus it becomes possible to acquire for longer t1 acquisition times without compromising the quality of homodecoupling. The mirror symmetric double perfect echo is implemented into the evolution period of a TOCSY experiment. A spin lock pulse purges undesired dispersive antiphase components at the end of the central t1 evolution period. Pure absorptive lineshapes with reduced proton spin multiplicities are obtained. The approach can be used in conjunction with real or constant time chemical shift evolution. In case of compounds with reduced T2 relaxation time, the real time approach is advisable, where the echo delays are an extension of the t1 evolution period. In this way, an unnecessary loss due to T2 relaxation is avoided. Using the pulse sequence in constant time mode at high t1max values gives ω1-homodecoupled TOCSY spectra without a significant dependence of the transfer amplitude on J. All experiments were carried out using non uniform sampling to decrease the measurement time. Experimental setup, advantages and limitations are discussed.

Near Resonant Optical Absorption by a System Coupled with Two Laser Beams

The structure of a solution of the generalized Maxwell–Bloch system of equations describing the strongly pumped interacting two-level atoms is discussed. This structure is represented by means of the corresponding differential equations for each contributing process. The interaction between the processes is introduced through the interaction integral and is illustrated by the specific system of graphs. The method allows one to describe the quantum-field-induced long-range interaction prevailing over short-range collisions and causing the broadening, narrowing, and shifts of an absorption line shape. The description is given in terms of the interaction integrals which couple the collective atomic polarization and population inversion. The contributions from different effects are analyzed with the use of the additivity of the corresponding absorption/reemission rates.

Theory of the absorption line shape in monolayers of transition metal dichalcogenides

The linear absorption spectra in monolayers of transition metal dichalcogenides show pronounced signatures of the exceptionally strong exciton-phonon interaction in these materials. To account for both exciton and phonon physics in such optical signals, we compare different theoretical methods to calculate the absorption spectra using the example of $\mathrm{MoSe_2}$. In this paper, we derive the equations of motion for the polarization either using a correlation expansion up to 4th Born approximation or a time convolutionless master equation. We show that the Born approximation might become problematic when not treated in high enough order, especially at high temperatures. In contrast, the time convolutionless formulation gives surprisingly good results despite its simplicity when compared to higher-order corrrelation expansion and therefore provides a powerful tool to calculate the lineshape of linear absorption spectra in the very popular monolayer materials.

Frenkel-Holstein Hamiltonian applied to absorption spectra of quaterthiophene-based 2D hybrid organic-inorganic perovskites.

For the prototypical two-dimensional hybrid organic-inorganic perovskites (2D HOIPs) (AE4T)PbX4 (X = Cl, Br, and I), we demonstrate that the Frenkel-Holstein Hamiltonian (FHH) can be applied to describe the absorption spectrum arising from the organic component. We first model the spectra using only the four nearest neighbor couplings between translationally inequivalent molecules in the organic herringbone lattice as fitting parameters in the FHH. We next use linear-response time-dependent density functional theory (LR-TDDFT) to calculate molecular transition densities, from which extended excitonic couplings are evaluated based on the atomic positions within the 2D HOIPs. We find that both approaches reproduce the experimentally observed spectra, including changes in their shape and peak positions. The spectral changes are correlated with a decrease in excitonic coupling from X = Cl to X = I. Importantly, the LR-TDDFT-based approach with extended excitonic couplings not only gives better agreement with the experimental absorption line shape than the approach using a restricted set of fitted parameters but also allows us to relate the changes in excitonic coupling to the underlying geometry. We accordingly find that the decrease in excitonic coupling from X = Cl to Br to I is due to an increase in molecular separation, which in turn can be related to the increasing Pb-X bond length from Cl to I. Our research opens up a potential pathway to predicting optoelectronic properties of new 2D HOIPs from ab initio calculations and to gain insight into structural relations from 2D HOIP absorption spectra.

Critical Test of the Interaction of Surface Plasmon Resonances with Molecular Vibrational Transitions.

We determine the infrared absorption spectra of a gas due to evanescent plasmonic electromagnetic fields in a system where surface interactions (physisorption and chemisorption) are demonstrably negligible. The plasmonic host material, the degenerate semiconductor CdO:Dy, has high mobility (366-450 cm2/(V s)) and carrier density ((0.6-3.5) × 1020 cm-3), and therefore supports low-loss surface plasmon resonances in the mid-IR. This high-mobility layer gives the highest resolution observed in a plasmonic conducting material in the infrared, higher than that of gold and rivaling that of silver. The high resolution permits a new understanding of the nature of the interaction of emerging fields with molecular transitions. Using different carrier concentrations, the resonance condition of the surface plasmon polariton (SPP) frequency (ωSPP) and N2O vibrational absorption spectral frequency (ωN2O) can be controlled, thereby allowing a critical test of field-molecule interactions. Experiment and theory both indicate a dispersive N2O line shape for ωSPP < ωN2O, an absorptive line shape for ωSPP < ωN2O, and an abrupt change between the two when the resonance condition ωSPP < ωN2O is reached. A first-order expansion of the Airy equation describes this behavior analytically. The SPP surface enhancement is 6.8 ± 0.5 on-resonance, lower than enhancements observed in other systems, but in agreement with recent quantitative reports of surface enhanced infrared reflection absorption spectroscopy (SEIRA). Our results show that interactions of infrared SPPs with molecular vibrations are in the weak coupling limit, and that enhancements comparable those reported for noble metals can be achieved.

Dephasing and Decoherence in Vibrational and Electronic Line Shapes

Absorption and emission line shapes of vibrational and electronic transitions in liquids are broadened by interactions with the "bath" (in this case, the rotational and translational degrees of freedom of all the molecules in the liquid). If these degrees of freedom are treated classically, the broadening process is often known as dephasing. If, on the other hand, the bath degrees of freedom are instead treated quantum mechanically, there is additional broadening due to what is known in the chemical-physics literature as decoherence. The question addressed in this paper is the relative importance of decoherence (bath quantum effects) and dephasing. We present general developments of this subject for absorption and emission line shapes, discover several new relationships connecting classical and quantum treatments of the bath, and also consider the Stokes shift (difference in peak frequencies in absorption and emission). We next draw some general conclusions by considering a model system whose transition-frequency time-correlation function has only one bath time scale. We then consider a realistic system of the vibrational OH stretch transition of dilute HOD in liquid D2O at room temperature. For this system, we conclude that bath quantum effects are not very important, except for the Stokes shift. More generally, we argue that this is the case for many vibrational and most electronic transitions in room-temperature liquids.

Comb-locked cavity ring-down spectroscopy with variable temperature.

Temperature dependence of molecular absorption line shape is important information for spectroscopic studies and applications. In this work, we report a comb-locked cavity ring-down spectrometer employing a cryogenic cooler to perform absorption spectroscopy measurements at temperatures between 40 K and 300 K. As a demonstration, we recorded the spectrum of the R(0) line in the (2-0) band of HD at 46 K. The temperature was also confirmed by the Doppler width of the HD line. Spectra of CH4 near 1.394 μm were also recorded in a wide temperature range of 70-300 K. Lower-state energies of methane lines were analyzed by fitting these spectra, which can be directly compared with the HITRAN and TheoReTS databases. Considerable deviations were observed, indicating the need to investigate the assignments of the methane lines in this region.

Effect of dimensionality on the optical absorption properties of CsPbI3 perovskite nanocrystals.

The bandgaps of CsPbI3 perovskite nanocrystals are measured by absorption spectroscopy at cryogenic temperatures. Anomalous bandgap shifts are observed in CsPbI3 nanocubes and nanoplatelets, which are modeled accurately by bandgap renormalization due to lattice vibrational modes. We find that decreasing dimensionality of the CsPbI3 lattice in nanoplatelets greatly reduces electron-phonon coupling, and dominant out-of-plane quantum confinement results in a homogeneously broadened absorption line shape down to cryogenic temperatures. An absorption tail forms at low-temperatures in CsPbI3 nanocubes, which we attribute to shallow defect states positioned near the valence band edge.

The Radiative Transfer Characteristics of the O2 Infrared Atmospheric Band in Limb-Viewing Geometry

The O2(a1Δg) emission near 1.27 μm provides an important means to remotely sense the thermal characteristics, dynamical features, and compositional structures of the upper atmosphere because of its photochemistry and spectroscopic properties. In this work, an emission–absorption transfer model for limb measurements was developed to calculate the radiation and scattering spectral brightness by means of a line-by-line approach. The nonlocal thermal equilibrium (non-LTE) model was taken into account for accurate calculation of the O2(a1Δg) emission by incorporating the latest rate constants and spectral parameters. The spherical adding and doubling methods were used in the multiple scattering model. Representative emission and absorption line shapes of the O 2 ( a 1 Δ g , υ ′ = 0 ) → O 2 ( X Σ g 3 , υ ″ = 0 ) band and their spectral behavior varying with altitude were examined. The effects of solar zenith angle, surface albedo, and aerosol loading on the line shapes were also studied. This paper emphasizes the advantage of using infrared atmospheric band for remote sensing of the atmosphere from 20 up to 120 km, a significant region where the strongest coupling between the lower and upper atmosphere occurs.

Two-photon resonances, ac Stark splittings, and shifts of the resonance peaks in Doppler free absorptive lineshapes of a double-lambda type four level system

Under Doppler free condition and by using semiclassical approach, a double-lambda type four-level system coupled to two electromagnetic fields are investigated. The coupled optical Bloch equations involving the density matrix elements in steady state are solved numerically to investigate the signal lineshapes as the function of signal detuning and pump Rabi-frequencies. The on-resonant pump leads to dynamic Stark splitting. The dent in the absorption lineshape is exhibited for off-resonant pump and is a signature of two-photon resonances. The appearance of extra absorption and emission peaks in the computed lineshapes are attributed by the nonlinear polarizations and hence the spontaneously generated coherences.

Anomalies in the switching dynamics of C -type antiferromagnets and antiferromagnetic nanowires

Antiferromagnets (AFMs) are widely believed to be superior than ferromagnets in spintronics because of their high stability due to the vanishingly small stray field. It is thus expected that the order parameter of AFM should always align along the easy-axis of the crystalline anisotropy. In contrast to this conventional wisdom, we find that the AFM order parameter switches away from the easy-axis below a critical anisotropy strength when an AFM is properly tailored into a nano-structure. The switching time first decreases and then increases with the damping. Above the critical anisotropy, the AFM order parameter is stable and precesses under a microwave excitation. However, the absorption peak is not at resonance frequency even for magnetic damping as low as 0.01. To resolve these anomalies, we first ascertain the hidden role of dipolar interaction that reconstructs the energy landscape of the nano-system and propose a model of damped non-linear pendulum to explain the switching behavior. In this framework, the second anomaly appears when an AFM is close to the boundary between underdamped and overdamped phases, where the observed absorption lineshape has small quality factor and thus is not reliable any longer. Our results should be significant to extract the magnetic parameters through resonance techniques.

Quantum dissipative systems beyond the standard harmonic model: Features of linear absorption and dynamics.

Current simulations of ultraviolet-visible absorption lineshapes and dynamics of condensed phase systems largely adopt a harmonic description to model vibrations. Often, this involves a model of displaced harmonic oscillators that have the same curvature. Although convenient, for many realistic molecular systems, this approximation no longer suffices. We elucidate nonstandard harmonic and anharmonic effects on linear absorption and dynamics using a stochastic Schrödinger equation approach to account for the environment. First, a harmonic oscillator model with ground and excited potentials that differ in curvature is utilized. Using this model, it is shown that curvature difference gives rise to an additional substructure in the vibronic progression of absorption spectra. This effect is explained and subsequently quantified via a derived expression for the Franck-Condon coefficients. Subsequently, anharmonic features in dissipative systems are studied, using a Morse potential and parameters that correspond to the diatomic molecule H2 for differing displacements and environment interaction. Finally, using a model potential, the population dynamics and absorption spectra for the stiff-stilbene photoswitch are presented and features are explained by a combination of curvature difference and anharmonicity in the form of potential energy barriers on the excited potential.

Enhancing off-axis integrated cavity output spectroscopy (OA-ICOS) with radio frequency white noise for gas sensing.

Injecting radio frequency (RF) white noise to the current driving of the laser can broaden the laser emission linewidth and efficiently suppress cavity-mode noise in off-axis integrated cavity output spectroscopy (OA-ICOS). The effect of the injected RF noise level on the cavity-mode noise and the deformation of the absorption line shape in off-axis integrated cavity output spectroscopy (OA-ICOS) with a distributed feedback laser (DFB) at 1.65 µm were investigated. We measured methane at different concentrations between 0.1 ppmv and 2 ppmv associated with a -20 dBm RF noise injection. A linear spectral response of the intensity of the cavity output spectra with the CH4 concentration was observed. A threefold improvement in the detection limit was achieved compared to unperturbed OA-ICOS. The response time of the improved OA-ICOS system is about 30 s and the minimum detectable concentration (MDC) of CH4 is 7.6 ppbv, which corresponds to a minimum detectable fractional absorption scaled to the path length of 7.3 × 10-10 cm-1. The noise equivalent absorption sensitivity of the system is 5.51 × 10-9 cm-1Hz-1/2.