Line Shape Studies Research Articles

Micro-lensing-induced line shapes in a single-mode cold-atom-hollow-core-fiber interface.

We report on the observation of strong transmission line shape alterations in a cold-atom-hollow-core-fiber interface. We show that this can lead to a significant overestimation of the assigned resonant optical depth for high atom densities. By modeling light beam propagation in an inhomogeneous dispersive medium, we attribute the observations to micro lensing in the atomic ensemble in combination with the mode selection of the atom-fiber interface. The approach is confirmed by studies of Rydberg electromagnetically induced transparency line shapes.

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

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

H NMR Studies on Water Dynamics in Functionalized Mesoporous Silica

Mesoporous silica MCM-41 is prepared, for which the inner surfaces are modified by 3-(aminopropyl)triethoxysilane (APTES) in a controlled manner. Nitrogen gas adsorpition yields a pore diameter of 2.2 nm for the APTES functionalized MCM-41. ²H nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy (BDS) provide detailed and consistent insights into the temperature-dependent reorientation dynamics of water in this confinement. We find that a liquid water species becomes accompanied by a solid water species when cooling through ~210 K, as indicated by an onset of bimodal Mesoporous silica MCM-41 is prepared, for which the inner surfaces are modified by 3-(aminopropyl)triethoxysilane (APTES) in a controlled manner. Nitrogen gas adsorpition yields a pore diameter of 2.2 nm for the APTES functionalized MCM-41. ²H nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy (BDS) provide detailed and consistent insights into the temperature-dependent reorientation dynamics of water in this confinement. We find that a liquid water species becomes accompanied by a solid water species when cooling through ~210 K, as indicated by an onset of bimodal ²H spin-lattice relaxation. The reorientation of the liquid water species is governed by pronounced dynamical heterogeneity in the whole temperature range. Its temperature dependence shows a mild dynamic crossover when the solid water species emerges and, hence, the volume accessible to the liquid water species further shrinks. Therefore, we attribute this variation in the temperature dependence to a change from bulk-like behavior towards interface-dominated dynamics. Below this dynamic crossover, ²H line-shape and stimulted-echo studies show that water reorientation becomes anisotropic upon cooling, suggesting that these NMR approaches, but also BDS measurements do no longer probe the structural (α) relaxation, but rather a secondary (β) relaxation of water at sufficiently low temperatures. Then, another dynamic crossover at ~180 K can be rationalized in terms of a change of the temperature dependence of the β relaxation in response to a glassy freezing of the α relaxation of confined water. Comparing these results for APTES modied MCM-41 with previous findings for mesoporous silica with various pore diameters, we obtain valuable information about the dependence of water dynamics in restricted geometries on the size of the nanoscopic confinements and the properties of the inner surfaces. ²H spin-lattice relaxation. The reorientation of the liquid water species is governed by pronounced dynamical heterogeneity in the whole temperature range. Its temperature dependence shows a mild dynamic crossover when the solid water species emerges and, hence, the volume accessible to the liquid water species further shrinks. Therefore, we attribute this variation in the temperature dependence to a change from bulk-like behavior towards interface-dominated dynamics. Below this dynamic crossover, ²H line-shape and stimulted-echo studies show that water reorientation becomes anisotropic upon cooling, suggesting that these NMR approaches, but also BDS measurements do no longer probe the structural (α) relaxation, but rather a secondary (β) relaxation of water at sufficiently low temperatures. Then, another dynamic crossover at ~180 K can be rationalized in terms of a change of the temperature dependence of the β relaxation in response to a glassy freezing of the α relaxation of confined water. Comparing these results for APTES modied MCM-41 with previous findings for mesoporous silica with various pore diameters, we obtain valuable information about the dependence of water dynamics in restricted geometries on the size of the nanoscopic confinements and the properties of the inner surfaces.

2H NMR Studies on Water Dynamics in Functionalized Mesoporous Silica

Abstract Mesoporous silica MCM-41 is prepared, for which the inner surfaces are modified by 3-(aminopropyl)triethoxysilane (APTES) in a controlled manner. Nitrogen gas adsorpition yields a pore diameter of 2.2 nm for the APTES functionalized MCM-41. 2H nuclear magnetic resonance (NMR) and broadband dielectric spectroscopy (BDS) provide detailed and consistent insights into the temperature-dependent reorientation dynamics of water in this confinement. We find that a liquid water species becomes accompanied by a solid water species when cooling through ~210 K, as indicated by an onset of bimodal 2H spin-lattice relaxation. The reorientation of the liquid water species is governed by pronounced dynamical heterogeneity in the whole temperature range. Its temperature dependence shows a mild dynamic crossover when the solid water species emerges and, hence, the volume accessible to the liquid water species further shrinks. Therefore, we attribute this variation in the temperature dependence to a change from bulk-like behavior towards interface-dominated dynamics. Below this dynamic crossover, 2H line-shape and stimulted-echo studies show that water reorientation becomes anisotropic upon cooling, suggesting that these NMR approaches, but also BDS measurements do no longer probe the structural (α) relaxation, but rather a secondary (β) relaxation of water at sufficiently low temperatures. Then, another dynamic crossover at ~180 K can be rationalized in terms of a change of the temperature dependence of the β relaxation in response to a glassy freezing of the α relaxation of confined water. Comparing these results for APTES modied MCM-41 with previous findings for mesoporous silica with various pore diameters, we obtain valuable information about the dependence of water dynamics in restricted geometries on the size of the nanoscopic confinements and the properties of the inner surfaces.

Theory of ferromagnetic resonance driven by the combined action of spin-transfer torque and voltage-controlled magnetic anisotropy

An analytical study of the spectral line shape of ferromagnetic resonance (FMR) detected by spin rectification effect and driven by the combined action of spin-transfer torque (STT) and voltage-controlled magnetic anisotropy (VCMA) is developed. The system under consideration consists of a magnetic tunnel junction (MTJ). Explicit expressions for the symmetric and asymmetric components of the rectified voltage are derived, where the role of the VCMA, in-plane STT, and field-like torque is clearly identified and discussed. Typical geometrical configurations are particularly analyzed and compared with recent experimental results. The analytical findings show that the change of sign in the FMR response upon reversal of the magnetization is completely due to VCMA. By distinguishing in-plane, out-of-plane, and full magnetization reversal processes, it is shown that the VCMA induces a change of sign in the symmetric part for the in-plane and out-of-plane magnetization reversal, while the asymmetric part change its sign under a full and in-plane reversion of the magnetization. Explicit expressions of the symmetric and asymmetric contributions of the spectral line shape allow us to detect under what conditions the STT and VCMA can increase or decrease the FMR spectral line shape. The proposed theory allows access to a better understanding of the physics behind ferromagnetic resonance phenomena, promoting potential applications in STT+VCMA-based MTJs.

On the Better Understanding of the Surprisingly High Performance of Metal-Organic Framework-Based Mixed-Matrix Membranes Using the Example of UiO-66 and Matrimid.

Metal-organic frameworks feature a certain framework flexibility, mainly due to a linker mobility inside the lattice. The latter is responsible for effects like breathing or gate-opening, thus making predictions of the sorption and diffusion behavior quite difficult. Permeation measurements on supported UiO-66 membranes at low temperatures and on polymer-coated UiO-66 membrane layers as well as 2H NMR line shape studies and nitrogen sorption measurements of UiO-66 with deuterated linkers in Matrimid as mixed-matrix membranes (MMM) indicate that the 2-site 180° flips (π-flips) of the aromatic ring are hindered by the presence of (i) the surrounding polymer Matrimid and (ii) residual solvent molecules, thus giving profound insights into the molecular understanding of gas transport through metal-organic framework-based MMMs.

14N NQR lineshape in nanocrystals: An ab initio investigation of urea.

14N nuclear quadrupole resonance (NQR) lineshapes mostly contain information of low interest, although in nanocrystals they may display some unexpected behaviour. In this work, we present an ab initio computational study of the 14N NQR lineshapes in urea nanocrystals as a function of the nanocrystal size and geometry, focusing on the surface induced broadening of the lineshapes. The lineshapes were obtained through a calculation of the electric field gradient for each nitrogen site in the nanocrystal separately, taking into account the individual crystal field by embedding the molecule of interest in a suitable lattice of point multipoles representing other urea molecules in the nanocrystal. The small influence of distant molecules is found with a series expansion, using the in-crystal Sternheimer shieldings which we also calculated ab initio. We have considered nanocrystals with two geometries: a sphere and a cube, with characteristic sizes between 5 and 100 nm. Our calculations suggest that there is a dramatic difference between the linewidths for the two geometries. For spheres, we find a steep drop in linewidths at ∼10 nm; at 5 nm the linewidth is ∼11 kHz, whereas for sizes above 20 nm the linewidth is practically negligible (<100 Hz). For cubes, on the other hand, we find a steady 1/size decrease, from 12 kHz at 10 nm to 1.2 kHz at 100 nm. This analysis is important for 14N NQR spectroscopy of crystalline pharmaceuticals, where nanoparticles are increasingly more often embedded in some sort of matrix. Although this is only a theoretical analysis, we believe that this work can serve as a guidance for the forthcoming experimental analysis.

XXIII International Conference on Spectral Line Shapes

23rd International Conference on Spectral Line Shapes (ICSLS)The 23rd ICSLS was held in Toruń, Poland, from Sunday, June 19 to Friday, June 24, 2016 in newly built The Culture and Congress Centre - Jordanki. The Conference was attended by 99 participants representing 60 research and academic institutions as well as high-tech companies from 19 different countries. The conference covered a broad range of topics related to spectral line shape studies, including: line shapes of atomic and molecular transitions in neutral gaseous mixtures, high and low temperature plasmas, clusters and helium droplets, spectroscopy of stellar atmospheres and interstellar media, spectroscopy of planetary atmospheres and exoplanets, cold atoms and molecules, collision-induced spectra, processes in laser fields, innovative techniques of line shape applications for diagnostic purposes and fundamental studies with narrow optical resonances.

Spectral line-shape study by cavity-enhanced complex refractive index spectroscopy

We present a unique experimental setup that enables measurement of high-resolution complex refractive index spectra of gas sample using several cavity-enhanced methods: frequency-stabilized cavity ring-down spectroscopy, cavity mode-width spectroscopy and one-dimensional cavity mode-dispersion spectroscopy. Presented examples of applications cover molecular spectral line-shape investigations, line intensities and unperturbed line center frequency measurements and high-precision detection of systematic instrumental errors of various spectroscopic methods.

Amplification or cancellation of Fano resonance and quantum confinement induced asymmetries in Raman line-shapes.

Fano resonance is reported here to be playing a dual role by amplifying or compensating for the quantum confinement effect induced asymmetry in Raman line-shape in silicon (Si) nanowires (NWs) obtained from heavily doped n- and p-type Si wafers respectively. The compensatory nature results in a near symmetric Raman line-shape from heavily doped p-type Si nanowires (NWs) as both the components almost cancel each other. On the other hand, the expected asymmetry, rather with enhancement, has been observed from heavily doped n-type SiNWs. Such a system (p- & n-) dependent Raman line-shape study has been carried out by theoretical line-shape analysis followed by experimental validation through suitably designed experiments. A dual role of Fano resonance in n- and p-type nano systems has been observed to modulate Raman spectra differently and reconcile accordingly to enhance and cease the Raman spectral asymmetry respectively. The present analysis will enable one to be more careful while analyzing a symmetric Raman line-shape from semiconductor nanostructures.

Spectroscopic line parameters of 12CH4 for atmospheric composition retrievals in the 4300–4500 cm−1 region

Due to the importance of methane as a trace atmospheric gas and a greenhouse gas, we have carried out a precise line-shape study to obtain the CH4–CH4 and CH4–air half-width coefficients, CH4–CH4 and CH4–air shift coefficients and off-diagonal relaxation matrix element coefficients for methane transitions in the spectral range known as the “methane Octad”. In addition, the associated temperature dependences of these coefficients have been measured in the 4300–4500cm−1 region of the Octad. The high signal to noise ratio spectra of pure methane and of dilute mixtures of methane in dry air with high resolution have been recorded at temperatures from 148K to room temperature using the Bruker IFS 125 HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California. The analysis of spectra was done using a multispectrum non-linear least-squares curve fitting technique. Theoretical calculations have been performed and the results are compared with the previously published line positions, intensities and with the line parameters available in the GEISA and HITRAN2012 databases.

One-dimensional cavity mode-dispersion spectroscopy for validation of CRDS technique

Detection of systematic errors of the measurement method is a demanding task, since it requires an independent, high-accuracy reference method for comparison. Here, we validate the cavity ring-down spectroscopy (CRDS) in relation to the one-dimensional cavity mode-dispersion spectroscopy (1D-CMDS). The complex line-shape function is used for the first time in the simultaneous analysis of absorptive and dispersive spectra and its potential in accurate line-shape studies is indicated. A new approach providing insensitivity of the 1D-CMDS to the drift of the laser-to-cavity locking point is demonstrated.

Temperature dependences of self- and N2-broadened line-shape parameters in the ν3 and ν5 bands of 12CH3D: Measurements and calculations

This paper presents the results of a spectroscopic line shape study of self- and nitrogen-broadened 12CH3D transitions in the ν3 and ν5 bands in the Triad region. We combined five pure gas spectra with eighteen spectra of lean mixtures of 12CH3D and nitrogen, all recorded with a Bruker IFS-125 HR Fourier transform spectrometer. The spectra have been analyzed simultaneously using a multispectrum nonlinear least squares fitting technique. N2-broadened line parameters for 184 transitions in the ν3 band and 205 transitions in the ν5 band were measured. In addition, line positions and line intensities were measured for 168 transitions in the ν3 band and 214 transitions in the ν5 band. We have observed 10 instances of weak line mixing corresponding to K″=3 A1 or A2 transitions. Comparisons were made for the N2-broadening coefficients and associated temperature exponents with corresponding values calculated using a semi-classical Robert Bonamy type formalism that involved an inter-molecular potential with terms corresponding to short- and long-range interactions, and exact classical molecular trajectories. The theoretical N2-broadened coefficients are overestimated for high J values, but are in good agreement with the experimental values for small and middle range J values.

Numerical Study of Spectral Line Shapes in High-Density He Plasmas

Numerical Study of Spectral Line Shapes in High-Density He Plasmas

EIT line shape in an open and partially closed multilevel V-type system

A detail theoretical analysis based on density matrix formulation is carried out to study the electromagnetically induced transparency in a multilevel open V-type system. The density matrix equations are solved numerically for both the Doppler-free and Doppler-broadened medium. We get two coherent electromagnetically induced transparency (EIT) peaks of sub-natural line width and five saturation peaks of sub-Doppler line width. The effect of decoherence on the EIT peak is studied using the theoretical model. A comparative study of the EIT line shape for open and closed V-type system has been done using the theoretical results. In our experiment, we have observed one EIT peak and four saturation peaks in an open V-type system corresponding to the D2 transition of 85Rb atoms and the EIT peak gets enhanced for partially closed V-type system compared to the open system. The dependence of height and width of the EIT line shape for different pump power values is also observed. The experimental observations are simulated numerically with a good agreement. We have also reported a noticeable change in the contrast of the EIT resonance due to the tuning of the pump laser frequency over the entire probe Doppler profile.

Oxovanadium(IV) complexes based on S-alkyl-thiosemicarbazidato ligands. Synthesis, characterization, electrochemical, and antioxidant studies

Reaction of VOSO4 with 2-hydroxy-napthaldeyde-S-R-thiosemicarbazones (R: methyl, ethyl, propyl or allyl) and salicyl aldehyde yielded five-coordinate oxovanadium(IV) complexes having a N1,N4-diarylidene-S-R-thiosemicarbazidato structures. The compounds were characterized by elemental analysis, magnetic measurements, electronic, infrared, 1H-NMR, and electron paramagnetic resonance (EPR) spectra. The X-band EPR signals were recorded from powder forms and also in solution. All the complexes have a single asymmetric line shape and theoretical fit studies prove the presence of axial symmetry around the paramagnetic vanadium ions. A computer simulation of the EPR spectrum of each complex was carried out to derive the related EPR parameters. Cyclic voltammograms of the complexes exhibited two metal-based reversible redox peaks around 500 and −800 mV corresponding to one electron oxidation/reduction of VIVO/VVO and VIVO/VIIIO, respectively. The reductive response in the 50–350 mV region was assigned to ligand reduction. Antioxidant activities of the compounds were determined with CUPric Reducing Antioxidant Capacity, 2,2-azino-bis-3-ethylbenzothiazoline-6-sulfonic acid, and 1,1-diphenyl-2-picrylhydrazyl assays. The test results indicated that the antioxidant capacity of the compounds increases with the carbon number of saturated hydrocarbon chain on sulfur atom.

Self- and air-broadened line shapes in the 2ν3 P and R branches of 12CH4

In this paper we report line shape parameters of 12CH4 for several hundred 2ν3 transitions in the spectral regions 5891–5996cm−1 (P branch) and 6015–6115cm−1 (R branch). Air- and self-broadening coefficients were measured as a function of temperature; line mixing via off-diagonal relaxation matrix element coefficients was also obtained for 47 transition pairs. In total, nearly 1517 positions and intensities were retrieved, but many transitions were too weak for the line shape study. For this analysis, we used 25 high-resolution (0.0056 and 0.0067cm−1) and high signal-to-noise (S/N) spectra of high-purity 12CH4 and the same high-purity 12CH4 broadened by dry air recorded at different sample temperatures between 130K and 295K with the Bruker IFS 125HR Fourier transform spectrometer at JPL. Three different absorption cells were used (1) a White cell set to a path length of 13.09m for room temperature data, (2) a single-pass 0.2038m long coolable cell (for self-broadening) and (3) a multipass cell with 20.941m total path coolable Herriott cell (for air-broadening). In total there were 13 spectra with pure 12CH4 (0.27–599Torr) and 12 air-broadened spectra with total sample pressures of 80–805Torr and volume mixing ratios (VMR) of methane between 0.18 and 1.0. An interactive multispectrum nonlinear least-squares technique was employed to fit the individual P10–P1 and R0–R10 manifolds in all the spectra simultaneously. Results obtained from the present analysis are compared to other recent measurements.

Facilitating guest transport in clathrate hydrates by tuning guest-host interactions.

The understanding and eventual control of guest molecule transport in gas hydrates is of central importance for the efficient synthesis and processing of these materials for applications in the storage, separation, and sequestration of gases and natural gas production. Previously, some links have been established between dynamics of the host water molecules and guest-host hydrogen bonding interactions, but direct observation of transport in the form of cage-to-cage guest diffusion is still lacking. Recent calculations have suggested that pairs of different guest molecules in neighboring cages can affect guest-host hydrogen bonding and, therefore, defect injection and water lattice motions. We have chosen two sets of hydrate guest pairs, tetrahydrofuran (THF)-CO2 and isobutane-CO2, that are predicted to enhance or to diminish guest-host hydrogen bonding interactions as compared to those in pure CO2 hydrate and we have studied guest dynamics in each using (13)C nuclear magnetic resonance (NMR) methods. In addition, we have obtained the crystal structure of the THF-CO2 sII hydrate using the combined single crystal X-ray diffraction and (13)C NMR powder pattern data and have performed molecular dynamics-simulation of the CO2 dynamics. The NMR powder line shape studies confirm the enhanced and delayed dynamics for the THF and isobutane containing hydrates, respectively, as compared to those in the CO2 hydrate. In addition, from line shape studies and 2D exchange spectroscopy NMR, we observe cage-to-cage exchange of CO2 molecules in the THF-CO2 hydrate, but not in the other hydrates studied. We conclude that the relatively rapid intercage guest dynamics are the result of synergistic guest A-host water-guest B interactions, thus allowing tuning of the guest transport properties in the hydrates by choice of the appropriate guest molecules. Our experimental value for inter-cage hopping is slower by a factor of 10(6) than a published calculated value.

Precise cavity enhanced absorption spectroscopy

A short review of recent achievements in high-precision cavity enhanced absorption spectroscopy is presented. Actual challenges and development paths in modern line shape study are indicated and discussed. The importance of identification and quantification of systematic instrumental errors affecting the measured line shape is highlighted. New, alternative measurement methods based on cavity enhanced spectroscopy are proposed.

Alternative approaches to cavity enhanced absorption spectroscopy

New approaches to cavity enhanced absorption spectroscopy are presented. They are based on precise measurements of shape of cavity modes broadened and shifted in the vicinity of the absorber placed inside the high-finesse cavity. The usefulness of both techniques to accurate line-shape study is demonstrated on an example of a weak (3 ← 0) 13C16O transition.