Lorentzian Width Research Articles

High steady-state column density of I((2)P3/2) atoms from I2 photodissociation at 532 nm: Towards parity non-conservation measurements.

Steady-state column densities of 1017 cm−2 of I(2P3/2) atoms are produced from photodissociation of I2 vapour at 290.5 K using 5 W of 532 nm laser light. Recombination of the I(2P3/2) atoms at the cell walls is minimized by coating the cell surface with a hydrophobic silane (dimethyldichlorosilane/DMDCS). Operation at room temperature, and at an I2 vapour pressure of ~0.2 mbar, without using a buffer gas, allows relatively low Lorentz and Doppler widths of ~2π × 1.5 (FWHM) and ~2π × 150 (HW at 1/e2) Mrad/s, respectively, at the M1 transition of atomic iodine at 1315 nm. These high column densities and low linewidths are favorable for parity nonconservation optical rotation measurements near this M1 transition. Furthermore, as the cell is completely sealed, this method of production of high-density 127I(2P3/2) atoms is also compatible with using iodine radioisotopes, such as for the production of high-density 129I(2P3/2).

Raman Spectra of Crystalline Double Calcium Orthovanadates Ca10M(VO4)7 (M = Li, K, Na) and Their Interpretation Based on Deconvolution Into Voigt Profiles

Unpolarized spontaneous Raman spectra of crystalline double calcium orthovanadates Ca10M(VO4)7 (M = Li, K, Na) in the range 150–1600 cm–1 were measured. Two vibrational bands with full-width at half-maximum (FWHM) of 37–50 cm–1 were found in the regions 150–500 and 700–1000 cm–1. The band shapes were approximated well by deconvolution into Voigt profiles. The band at 700–1000 cm–1 was stronger and deconvoluted into eight Voigt profiles. The frequencies of two strong lines were ~848 and ~862 cm–1 for Ca10Li(VO4)7; ~850 and ~866 cm–1 for Ca10Na(VO4)7; and ~844 and ~866 cm–1 for Ca10K(VO4)7. The Lorentzian width parameters of these lines in the Voigt profiles were ~5 times greater than those of the Gaussian width parameters. The FWHM of the Voigt profiles were ~18–42 cm–1. The two strongest lines had widths of 21–25 cm–1. The vibrational band at 300–500 cm–1 was ~5–6 times weaker than that at 700–1000 cm–1 and was deconvoluted into four lines with widths of 25–40 cm–1. The large FWHM of the Raman lines indicated that the crystal structures were disordered. These crystals could be of interest for Raman conversion of pico- and femtosecond laser pulses because of the intense vibrations with large FWHM in the Raman spectra.

Neutron Scattering Studies of Lithium-Ion Diffusion in Ternary Phosphate Glasses

We have studied the diffusion mechanism of lithium ions in glassy oxide-based solid state electrolytes using elastic and quasielastic neutron scattering. Samples of xLi 2 SO 4 -(1-x)(Li 2 O-P 2 O 5 ) were prepared using conventional melt techniques. Elastic and inelastic scattering measurements were performed using the triple-axis spectrometer (TRIAX) at Missouri University Research Reactor at University of Missouri and High Flux Backscattering Spectrometer (HFBS) at NIST Center for Neutron Research, respectively. These compounds have a base glass compound of P 2 O 5 which is modified with Li 2 O. Addition of Li 2 SO 4 leads to the modification of the structure and to an increase lithium ion (Li + ) conduction. We find that an increase of Li 2 SO 4 in the compounds leads to an increase in the Lorentzian width of the fit for the quasielastic data, which corresponds to an increase in Li + diffusion until an over-saturation point is reached ( 2 SO 4 ). We find that the hopping mechanism is best described by the vacancy mediated Chudley-Elliot model. A fundamental understanding of the diffusion process for these glassy compounds can help lead to the development of a highly efficient solid electrolyte and improve the viability of clean energy technologies.

Laser Linewidth and Spectral Resolution in Infrared Scanning Sum Frequency Generation Vibrational Spectroscopy System

Sum frequency generation vibrational spectroscopy (SFG-VS) is a robust technique for interfacial investigation at molecular level. The performance of SFG-VS mostly depends on the spectral resolution of the SFG system. In this research, a simplified function was deduced to calculate the spectral resolution of picosecond SFG system and the lineshape of SFG spectra based on the Guassian shaped functions of IR beam and visible beam. The function indicates that the lineshpe of SFG spectra from nonresonant samples can be calculated by the Guassian widths of both IR beam and visible beam. And the Voigt lineshape of SFG spectra from vibrational resonant samples can be calculated by the Homogeneous broadening (Lorentzian width) and Inhomogeneous broadening (Guassian width) of vibrational modes, as well as the Guassian widths of both IR beam and visible beam. Such functions were also applied to verify the spectral resolution of the polarization-resolved and frequency-resolved picosecond SFG-VS system which was developed by our group recently. It is shown that the linewidths of IR beams that generated from current laser system are about 1.5 cm−1. The calculated spectral resolution of current picosecond IR scanning SFG-VS system is about 4.6 cm−1, which is consist with he spctral resolution shown in the spectra of cholesterol monolayer (3.5–5 cm−1).

Broadening of CO2 lines in the 4.3 μm region by H2O

Transmission spectra of CO2 highly diluted in water vapor have been recorded at 50 and 95°C for four pressures between 0.02 and 0.1atm using a high resolution Fourier Transform spectrometer. The collisional (Lorentz) widths of many lines of the ν3 band (and of some of the ν3+ν2−ν2 hot band) have been retrieved from each spectrum through fits using Voigt line shapes. Our result are about 4% lower than the values recommended in a previous study but they confirm the relative variations of the line broadening on the rotational quantum numbers. We also provide the first determination of H2O-induced line shifts of CO2 lines.

Voigt deconvolution method and its applications to pure oxygen absorption spectrum at 1270 nm band

Experimental spectral lines of pure oxygen at 1270nm band were analyzed by Voigt deconvolution method. The method gave a total Voigt profile, which arises from two overlapping bands. Deconvolution of total Voigt profile leads to two Voigt profiles, the first as a result of O2 dimol at 1264nm band envelope, and the second from O2 monomer at 1268nm band envelope. In addition, Voigt profile itself is the convolution of Lorentzian and Gaussian distributions. Competition between thermal and collisional effects was clearly observed through competition between Gaussian and Lorentzian width for each band envelope. Voigt full width at half-maximum height (Voigt FWHM) for each line, and the width ratio between Lorentzian and Gaussian width (ΓLΓG−1) have been investigated. The following applied pressures were at 1, 2, 3, 4, 5, and 8bar, while the temperatures were at 298K, 323K, 348K, and 373K range.

A new, simple approximation for the deconvolution of instrumental broadening in spectroscopic band profiles.

A robust empirical correction formula has been developed for the approximation of Lorentzian widths, using a known spectrometer bandpass, in instrument-broadened Voigt bands in optical spectra. The relationship between analytically calculated [(w(Voigt) - w(Lorentz))/w(Gauss)] and [w(Voigt)/w(Gauss) - 1] values (where w is the full width at half-maximum [FWHM]) is analyzed to derive the formula for the approximation of the (w(Voigt) - w(Lorentz)) difference. The precision of the method is demonstrated by comparing its performance to several previously published numerical correction approaches. The fraction of the Lorentzian contribution in Voigt FWHMs is evaluated in terms of the Gaussian FWHM to assess the conditions under which the deconvolution of instrumental broadening is necessary.

Self-broadening of 16O12C16O ν3-band lines

Absorption spectra of pure 16O12C16O have been recorded, at room temperature and for five pressures between 0.2 and 1atm, in the very intense ν3 band. As recently done for CO, this was achieved using a high resolution (0.005cm−1) Fourier transform spectrometer together with a specially designed cell. With the latter, set to a path length of about 20μm, the absorption by extremely intense lines is measured under appropriate (non saturating transmission) absorption conditions, regardless of the gas pressure. The recorded spectra have been adjusted one-by-one using Voigt line-shapes in order to retrieve the line positions and the Lorentz widths for the P(40) to R(40) lines. The results show that accurate self-broadening coefficients γ are obtained but that experimental uncertainties forbid any reliable determinations of the pressure-induced shifts δ due to the fact that they are about two order of magnitude smaller than γ. The present values of γ show the limited accuracy of previous determinations for the exact same lines. They are in very good agreement with those in the HITRAN database if the latter, which are for a speed-dependent Voigt profile, are properly corrected to correspond to a Voigt profile.

Line shape parameters of PH3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence

Accurate knowledge of spectroscopic line parameters of PH3 is important for remote sensing of the outer planets, especially Jupiter and Saturn. In a recent study, line positions and intensities for the Pentad bands of PH3 have been reported from analysis of high-resolution, high signal-to noise room-temperature spectra recorded with two Fourier transform spectrometers (2014) [1]. The results presented in this study were obtained during the analysis of positions and intensities, but here we focus on the measurements of spectral line shapes (e.g. widths, shifts, line mixing) for the 2ν4, ν2+ν4, ν1 and ν3 bands. A multispectrum nonlinear least squares curve fitting technique employing a non-Voigt line shape to include line mixing and speed dependence of the Lorentz width was employed to fit the spectra simultaneously. The least squares fittings were performed on five room-temperature spectra recorded at various PH3 pressures (∼2–50Torr) with the Bruker IFS-125HR Fourier transform spectrometer (FTS) located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington. Over 840 Lorentz self-broadened half-width coefficients, 620 self-shift coefficients and 185 speed dependence parameters were measured. Line mixing was detected for transitions in the 2ν4, ν1 and ν3 bands, and their values were quantified for 10 A+A− pairs of transitions via off-diagonal relaxation matrix element formalism. The dependences of the measured half-width coefficients on the J and K rotational quanta of the transitions are discussed. The self-width coefficients for the ν1 and ν3 bands from this study are compared to the self-width coefficients for transitions with the same rotational quanta (J, K) reported for the Dyad (ν2 and ν4) bands. The measurements from present study should be useful for the development of a reliable theoretical modeling of pressure-broadened widths, shifts and line mixing in symmetric top molecules with C3v symmetry in general, and of PH3 in particular.

Excited-State Structure, Vibrations, and Nonradiative Relaxation of Jet-Cooled 5-Fluorocytosine

The S0 → S1 vibronic spectrum and S1 state nonradiative relaxation of jet-cooled keto-amino 5-fluorocytosine (5FCyt) are investigated by two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm(–1) resolution. The 0(0)(0) rotational band contour is polarized in-plane, implying that the electronic transition is (1)ππ*. The electronic transition dipole moment orientation and the changes of rotational constants agree closely with the SCS-CC2 calculated values for the (1)ππ* (S1) transition of 5FCyt. The spectral region from 0 to 300 cm(–1) is dominated by overtone and combination bands of the out-of-plane ν1′ (boat), ν2′ (butterfly), and ν3′ (HN–C6H twist) vibrations, implying that the pyrimidinone frame is distorted out-of-plane by the (1)ππ* excitation, in agreement with SCS-CC2 calculations. The number of vibronic bands rises strongly around +350 cm(–1); this is attributed to the (1)ππ* state barrier to planarity that corresponds to the central maximum of the double-minimum out-of-plane vibrational potentials along the ν1′, ν2′, and ν3′ coordinates, which gives rise to a high density of vibronic excitations. At +1200 cm(–1), rapid nonradiative relaxation (k(nr) ≥ 10(12) s(–1)) sets in, which we interpret as the height of the (1)ππ* state barrier in front of the lowest S1/S0 conical intersection. This barrier in 5FCyt is 3 times higher than that in cytosine. The lifetimes of the ν′ = 0, 2ν1′, 2ν2′, 2ν1′ + 2ν2′, 4ν2′, and 2ν1′ + 4ν2′ levels are determined from Lorentzian widths fitted to the rotational band contours and are τ ≥ 75 ps for ν′ = 0, decreasing to τ ≥ 55 ps at the 2ν1′ + 4ν2′ level at +234 cm(–1). These gas-phase lifetimes are twice those of S1 state cytosine and 10–100 times those of the other canonical nucleobases in the gas phase. On the other hand, the 5FCyt gas-phase lifetime is close to the 73 ps lifetime in room-temperature solvents. This lack of dependence on temperature and on the surrounding medium implies that the 5FCyt nonradiative relaxation from its S1 ((1)ππ*) state is essentially controlled by the same ~1200 cm(–1) barrier and conical intersection both in the gas phase and in solution.

CO2 isolated line shapes by classical molecular dynamics simulations: Influence of the intermolecular potential and comparison with new measurements

Room temperature absorption spectra of various transitions of pure CO2 have been measured in a broad pressure range using a tunable diode-laser and a cavity ring-down spectrometer, respectively, in the 1.6 μm and 0.8 μm regions. Their spectral shapes have been calculated by requantized classical molecular dynamics simulations. From the time-dependent auto-correlation function of the molecular dipole, including Doppler and collisional effects, spectral shapes are directly computed without the use of any adjusted parameter. Analysis of the spectra calculated using three different anisotropic intermolecular potentials shows that the shapes of pure CO2 lines, in terms of both the Lorentz widths and non-Voigt effects, slightly depend on the used potential. Comparisons between these ab initio calculations and the measured spectra show satisfactory agreement for all considered transitions (from J = 6 to J = 46). They also show that non-Voigt effects on the shape of CO2 transitions are almost independent of the rotational quantum number of the considered lines.

Development of a high dynamic range spectroscopic system for observation of neutral hydrogen atom density distribution in Large Helical Device core plasma

We report development of a high dynamic range spectroscopic system comprising a spectrometer with 30% throughput and a camera with a low-noise fast-readout complementary metal-oxide semiconductor sensor. The system achieves a 10(6) dynamic range (∼20 bit resolution) and an instrumental function approximated by a Voigt profile with Gauss and Lorentz widths of 31 and 0.31 pm, respectively, for 656 nm light. The application of the system for line profile observations of the Balmer-α emissions from high temperature plasmas generated in the Large Helical Device is also presented. In the observed line profiles, emissions are detected in far wings more than 1.0 nm away from the line center, equivalent to neutral hydrogen atom kinetic energies above 1 keV. We evaluate atom density distributions in the core plasma by analyzing the line profiles.

Atmospheric helium capillary dielectric barrier discharge for soft ionization: broadening of spectral lines, gas temperature and electron number density

The capillary helium dielectric barrier discharge (DBD) operating at atmospheric pressure was investigated by means of optical emission spectroscopy with the aim to determine the dominant broadening mechanism of the helium spectral lines, gas temperature and electron number density. The dependence of emission profiles of helium 388 nm, 501 nm, 587 nm, 667 nm, 706 nm and 728 nm lines on discharge voltage, helium pressure and position along the DBD capillary was investigated. Also, the pressure and voltage dependence of the profiles of hydrogen H-alpha and H-beta lines was examined. The Lorentzian widths of the normalized helium line profiles were found to be constant with respect to the applied voltage and the position along the capillary. The dominant broadening mechanism for all investigated lines was identified to be due to collisions with ground-state helium atoms, with the Stark broadening being negligible. It was determined that the temperature of the gas was constant along the capillary and independent of the voltage applied on the DBD electrodes and that its value coincided with the room temperature. The measurements of the dependence of the Lorentzian width of hydrogen H-alpha and H-beta lines on helium pressure, combined with gas temperature determined in the experiment, yielded the following values for the broadening parameters due to broadening by neutral helium: γνHe(Hα) = 1.56 × 10−9 cm3 s−1 and γνHe(Hβ) = 3.16 × 10−9 cm3 s−1. From the analysis of the measured H-alpha and H-beta line profiles the upper limit of the electron number density in the investigated plasma was obtained as ne ≤ 1.4× 1012 cm−3.

Resonance and decay phenomena lead to quantum mechanical time asymmetry

The states (Schrödinger picture) and observables (Heisenberg picture) in the standard quantum theory evolve symmetrically in time, given by the unitary group with time extending over −∞ < t < +∞. This time evolution is a mathematical consequence of the Hilbert space boundary condition for the dynamical differential equations. However, this unitary group evolution violates causality. Moreover, it does not solve an old puzzle of Wigner: How does one describe excited states of atoms which decay exponentially, and how is their lifetime τ related to the Lorentzian width Γ? These question can be answered if one replaces the Hilbert space boundary condition by new, Hardy space boundary conditions. These Hardy space boundary conditions allow for a distinction between states (prepared by a preparation apparatus) and observables (detected by a registration apparatus). The new Hardy space quantum theory is time asymmetric, i.e, the time evolution is given by the semigroup with t0 ≤ t < +∞, which predicts a finite "beginning of time" t0, where t0 is the ensemble of time at which each individual system has been prepared. The Hardy space axiom also leads to the new prediction: the width Γ and the lifetime τ are exactly related by τ = ℏ/Γ.

Epitaxial Graphene on Si(111) Substrate Grown by Annealing 3C-SiC/Carbonized Silicon

High-quality epitaxial graphene has been a continuous focus of research interest owing to its viable device applications. Epitaxial graphene growth on silicon (Si) substrates is of great interest for its application to electronics. Here, we report experimental findings of atmospheric-pressure-grown epitaxial graphene on 3C-SiC(111)/carbonized Si(111) substrates. X-ray photoelectron spectroscopy and Raman spectroscopy were used for surface structural analysis and graphitic composition analysis. A Raman mapping image of the Lorentzian width of the 2D peak of graphene grown at 1300 °C signals the coexistence of single layers and multilayers. Transmission electron microscopy also confirmed the existence of monolayer graphene.

Scanning gate microscopy simulations for quantum rings: Effective potential of the tip and conductance maps

We simulate electron flow through a semiconductor quantum ring perturbed by a charged tip of a scanning microscope. We describe the interaction of the tip with the electron gas solving the density functional theory equations for up to several hundred electrons forming the background potential for the current flow at the Fermi level. The screening of the repulsive tip potential involves an appearance of the Friedel oscillations of the electron density. The effective potential of the tip turns out to be anisotropic and close to a Lorentzian along the channel. The Lorentzian width along the channel is comparable to the distance between the tip and the electron gas. The width is insensitive to the charge of the tip and the electron density. We discuss the conductance maps as calculated in the Landauer approach including the case when the tip is outside the ring. We discuss both the case of weak perturbation introduced by the tip in the context of extraction of the local density of states as well as the case of strong tip-electron-gas interaction, which modifies the potential landscape within the structure. For strong perturbation we find that the repulsive tip introduces radial fringes of conductance within the ring and concentric ones outside the ring. The radial ones correspond to interrupted current circulation around the ring and are insensitive to the external magnetic field while the external concentric fringes evolve in external magnetic field due to an interplay of the electrostatic and magnetic Aharonov-Bohm effects.

Monitoring Hydrogen Sulfide Using a Quantum Cascade Laser Based Trace Gas Sensing System

We present the detection of hydrogen sulfide (H2S) in a quantum cascade laser (QCL) based gas sensing system employing direct laser absorption spectroscopy. The sensitivity is obtained to be 3.61 × 10−6 cm−1 Hz−1/2 and the H2S broadening coefficient in N2 is analyzed by fitting to the plot of the Lorentzian half width at the half maximum as a function of N2 pressure is 0.1124 ± 0.0031 cm−1·atm−1. A simulation based on data from the HITRAN database shows broad agreement with the experimentally obtained spectrum.

Partially coherent Lorentz Gaussian beam and its scintillations

We study the scintillation aspects of partially coherent Lorentz Gaussian (LG) beams via numerically integrating the average and average squared intensity expressions. Within the examined range of input and propagation medium parameters, the LG beams are generally found to offer less and less scintillations against the pure Gaussian beam, particularly when the Lorentzian feature of the beam is emphasized more. This lower scintillation property is exhibited for collimated coherent beams with different Lorentz widths and at on-axis and off-axis positions of the receiver plane. When focusing is introduced, at shorter propagation distances the ordering of the beams remains as described above, but at longer propagations distances a complete reversing of the beam order is observed. Raising the turbulence levels by increasing the structure constant inevitably causes rises in scintillations, while preserving the advantage of LG beams over the pure Gaussian beam. Partial coherence reduces scintillations as expected, at the same time nearly eliminating the scintillation differences between the beam types.

Structure and Dynamics of a Thermoresponsive Microgel around Its Volume Phase Transition Temperature

Sustained drug delivery requires the use of multifunctional devices with enhanced properties. These properties include responsiveness to external stimuli (such as temperature, pH, ionic strength), ability to deliver suitably designed ligands to specific receptors, enhanced bioadhesion to cells, and cytocompatibility. Microgels represent one of such multifunctional drug delivery devices. Recently, we described the fabrication of a stable colloidal aqueous suspension of cytocompatible microgel spheres based on a poly(vinyl alcohol)/poly(methacrylate-co-N-isopropylacrylamide) network ( Ghugare, S. Mozetic, P. Paradossi, G. Biomacromolecules 2009 , 10 , 1589 ). These microgel spheres undergo an entropy-driven volume phase transition around the physiological temperature, this phase transition being driven by the incorporation of NiPAAm residues in the network. In that study, the microgel was loaded with the anticancer drug doxorubicin. As the microgel shrank, a marked increase in the amount of doxorubicin released was noted. Indeed, dynamic light scattering measurements showed the diameter reduction to be about 50%. In the present paper, we focus on some fundamental issues regarding modifications of the hydrogel architecture at a nanoscopic level as well as of the diffusive behavior of water associated with the polymer network around the volume phase transition temperature (VPTT). Sieving and size exclusion effects were studied by laser scanning confocal microscopy with the microgel exposed to fluorescent probes with different molecular weights. Confocal microscopy observations at room temperature and at 40 degrees C (i.e., below and above the VPTT) provided an evaluation of the variation of the average pore size (from 5 nm to less than 3 nm). Using quasielastic neutron scattering (QENS) with the IRIS spectrometer at ISIS, UK, the diffusive behavior of water molecules closely associated to the polymer network around the VPTT was investigated. A clear change in the values of diffusion coefficient of bound water was observed at the transition temperature. In addition, the local dynamics of the polymer itself was probed using the QENS spectrometer SPHERES at FRM II, Germany. For this study, the microgel was swollen in D(2)O. An average characteristic distance of about 5 A for the localized chain motions was evaluated from the elastic incoherent structure factor (EISF) and from the Q-dependence of the Lorentzian width.

Spectral line shape profile of rovibrational transitions of CO embedded in p-H2 crystals studied by high resolution IR diode laser spectroscopy

Line profiles of rovibrational transitions of CO embedded in p-H(2) crystals were studied by high resolution midinfrared diode laser spectroscopy. The line profile analysis for the R(0)(parallel), R(0)(perpendicular), P(1)(parallel), and P(1)(perpendicular) transitions shows that spectral line shapes are well reproduced by a convolution of Gaussian and Lorentzian functions. The temperature dependence of the Lorentzian Gamma(L)(T) and Gaussian widths Gamma(G)(T) shows that there is a nonzero linewidth contribution to each at the T = 0 K limit. The main part of the Lorentzian width Gamma(L)(T = 0) shows anisotropy in the hcp structure and is explained by spontaneous decay of the rotational excited state energy to phonon modes. A smaller part of Gamma(L)(T = 0) is attributed to inhomogeneous broadening due to the point defects of other CO molecules in the crystal. On the other hand, the Gaussian width Gamma(G)(T = 0) is explained by inhomogeneous broadening due to dislocations. In the T > 0 region, Gamma(L)(T) shows strong temperature dependence but Gamma(G)(T) does not. The center frequencies of the R(0)(perpendicular) and P(1)(parallel) transitions show blueshifts and those of the R(0)(parallel) and P(1)(perpendicular) transitions show redshifts with increasing temperature. This phenomenon is explained by a decrease in the anisotropy in the crystal field, which is caused by the averaging of thermal lattice fluctuations. Furthermore, the contribution of vibration and rotation to the linewidth is discussed.