High-resolution measurements of line intensity, broadening and shift of CO around m

Fundamental spectroscopical parameters of CO₂ are reported using a high resolution, direct absorption spectrometer, based on a distributed feed-back diode laser emitting at 2 μm. Line intensity, self- and foreign broadening and shift, with N₂ and O₂ as foreign gases, have been measured with high accuracy in the combination band of CO₂, for 13 lines of the R branch, from R(22) up to R(46). Comparison with available data is made, when possible, and a generally good agreement has been found. Received: 24 April 1998 / Received in final form: 28 October 1998     

Predissociation resonances in CO and IBr. Smooth exterior scaling combined with the discrete variable representation

Smooth exterior scaling (SES) and the discrete variable representation (DVR) are combined to accurately compute predissociation resonances of a bound state non-adiabatically coupled to a dissociative state. For the CO( predissociation interaction good agreement is found with approaches based on optical potentials and complex scaling. The comparison is done both in the diabatic and the adiabatic representation. The effect of the coupling strength in the IBr predissociation interaction and the transition from the diabatic to the adiabatic picture was studied by computing resonances for coupling strengths from up to . The transition from weak (diabatic) to strong (adiabatic) coupling was clearly seen. The intermediate case leads to a complicated resonance distribution. Comparison was made with recent studies using pump-probe spectroscopy [M. Shapiro, M.J.J. Vrakking, A. Stolow, J. Chem. Phys. 110, 2465 (1999)]. It was found that the overall features of the experiment could be explained from the resonance distribution, but for a detailed comparison more accurate potential energy surfaces and couplings are needed. Received 12 July 1999 and Received in final form 6 December 1999     

A multispectrum fitting procedure to deduce molecular line parameters: Application to the 3-0 band of 12 C 16 O

To deduce accurate infrared molecular line parameters (positions at zero pressure, pressure-shifting and pressure-broadening coefficients, collisional narrowing coefficients, and intensities) from rovibrational spectra, an automatic method based upon a multispectrum fitting procedure has been set up, able to treat simultaneously several laboratory Fourier transform spectra. A validation of this method, using absorption spectra of the 3-0 vibrational band of CO around 6 350 cm^-1, already used to measure line intensities and self-broadening coefficients, is presented, and the advantages of the method are pointed out. The self-collisional narrowing of CO was observed and determined for the first time in Fourier transform spectra: β = 0.028±0.004 cm^-1 atm^-1 at about 296 K. Received 21 September 2000 and Received in final form 15 January 2001     

Cusp satellite bands in the spectrum of molecule

We report measurements and a theoretical explanation of the cusp-shaped satellite bands in the blue wing of the cesium D₂ resonance line which have been observed for the first time. The bands are identified as transitions where the upper state dissociates into the 6 ²P _3/2 + 6 ² S _1/2 atomic asymptote. The experiment has been performed using a standard absorption setup, computer controlled data acquisition and computer data processing. We have shown that the peculiar shape of the difference-potential curve is solely responsible for the spectrum containing the cusp-shaped satellite bands. The appearance of these satellite bands has been discussed and explained relating the theory of satellite bands to the catastrophe theory. The shape of the line wing and of the satellite bands have been calculated using the Fourier transform technique. To ensure a more stringent comparison between the experimental and the theoretical spectrum, we have analyzed and compared the derivatives of the measured and the calculated satellite band shape. On the contrary to the customary direct comparison between the measured and the calculated absorption coefficient, the derivative clearly shows all differences and resemblances between satellite band profiles. The degree of coincidence of the experimentally observed and the theoretically calculated satellite band shape can be used as an ultimate check on the assessment of the quality of potential-energy curves involved in the formation of satellite bands. Received: 1 October 1997 / Revised: 14 January 1998 / Accepted: 24 February 1998     

Diode laser spectroscopic measurement and impact theoretical analysis of collision broadening of acetylene band transitions

A near infrared diode laser spectrometer has been used for measurement of line shapes of the rotational transitions of the () overtone-combination band of acetylene perturbed by oxygen and air. Pressure-broadening coefficients and line strength parameters are extracted from least squares fitting of the spectra with Voigt profiles. A detailed calculation of pressure-broadening coefficients for the self, nitrogen and oxygen broadening cases has been performed by using semi-classical impact theory based on quadrupolar and dispersion interactions. The relative importance of the intermolecular interactions has been investigated and it is found that for these weak interaction cases dispersive terms have a dominant role in line broadening. This is more pronounced for the O₂-broadening case. We have included all the non-resonant terms till convergence is achieved. The cutoff parameter b₀ of the Anderson procedure has been determined separately for each non-resonant process. In order to include the orientation effect of the molecules at the moment of collision we have considered an average kinetic collision diameter which sets the lower limit of b₀. This improves the result considerably and the calculated values are close to the observed results. The J-dependence of the half width is also reported and shows decrease for large J-values. Received 24 November 1999     

Collisional broadening and shifting of ammonia absorption lines at 790 nm

By using a diode laser spectrometer based on a commercial heterostructure diode laser operating in free-running mode, line shape parameters of some ammonia ro-vibrational overtones at 790 nm have been measured at room temperature. These weak absorption lines have been detected by using the wavelength modulation spectroscopy technique with second-harmonic detection. The broadening and shifting coefficients have been obtained for ten absorption lines by fitting the collected second-harmonic absorption features and varying the pressure of different buffer gases. Received 13 February 2002 / Received in final form 18 September 2002 Published online 17 December 2002 RID="a" ID="a"e-mail: alex@ifam.pi.cnr.it     

Self- and foreign-broadening and shift coefficients for C2H2 lines at 1.54 μm

In this article we present experimental data for line parameters measurements of several transition lines of overtone bands of C₂H₂ at 1540 nm. The measurements were done with a spectrometer based on a semiconductor diode laser and a direct absorption spectroscopy scheme. Broadening and shift coefficients have been measured for the pure gas or in mixtures with N₂, O₂ and CO₂ as perturbing gas. Received 6 November 2000 and Received in final form 13 March 2001     

Frequency measurements in the b <Superscript>3</Superscript>Π(0<Subscript>u</Subscript><Superscript>+</Superscript>) - X <Superscript>1</Superscript>Σ<Subscript>g</Subscript><Superscript>+</Superscript> system of K<Subscript>2</Subscript>

Absolute transition frequencies of the b ³Π(0_u ⁺) - X ¹Σ_g ⁺ system of K₂ were measured in a molecular beam with Lamb dip absorption spectroscopy applying a frequency comb from a femtosecond pulsed laser. Both, K atoms and K₂ molecules are present in the beam and are expected to interact by collisions. The atoms can be deflected optically out of the beam, and thus the collision rate between K atoms and K₂ molecules is changed by about an order of magnitude. The molecular transition frequencies for low collisional rate are compared with those for high one. Limits for the collisional frequency shift within the beam are determined.     

Identification of structures in absorption spectrum of Kr-Xe gas mixtures close to the Xe resonance line at 146.96 nm

The origins of spectral structures that appear close to the Xe resonance line at 146.96 nm in absorption spectra of Kr gas with an admixture of Xe are discussed in this paper. It is shown that these structures can result from bound-bound and bound-free transitions in the Xe-Kr molecule between the ground state and the 1(³P₁) excited state, which both are weakly-bound. The depth of the excited state is estimated. An introduction of a hump on the 1(³P₁) state internuclear potential is suggested. Received 15 December 1999 and Received in final form 20 February 2000     

Cesium satellite band at 875.2 nm stemming from the Cs 2 0 g + (6 p 2 P 1/2 +6 s 2 S 1/2 ) state

We measured a very distinct satellite band at 875.2 nm between two resonance lines of cesium. Spectral simulation using Spies and Meyer [#!ref1!#] ab initio potential curves and an appropriate transition dipole moment function was compared with experimental profile. Implications of the investigated satellite band at 875.2 nm in the field of ultracold cesium atom collisions are discussed with a special emphasize to new possibilities of the photoassociation of two ground state atoms leading to the formation of ultracold intermediate long-range molecules. Received 07 March 2001 and Received in final form 14 May 2001     

High resolution polarization spectroscopy and laser induced fluorescence of CO<Subscript>2</Subscript> around 2μm

High resolution Infrared Polarisation Spectroscopy (IRPS) and Infrared Laser Induced Fluorescence (IRLIF) techniques were used to probe CO₂/N₂ binary gas mixture at atmospheric pressure and ambient temperature. The probed CO₂ molecules were prepared by laser excitation to an overtone and combination ro-vibrational state (12⁰1, J=15) of CO₂, centred at 4988.6612 cm^-1. IRPS and IRLIF line profiles were recorded for several CO₂/N₂ binary mixtures. The observed IRLIF line shapes have the expected Lorentzian form while the observed IRPS line shapes are narrower by a factor of two than those recorded with the IRLIF and appear to have a Lorentzian-cubed profile. The recorded line profiles provide measurements of the pressure-broadening coefficient directly at atmospheric pressure. The Full-Width-Half-Maxima (FWHM) pressure broadening coefficients are measured, based on IRLIF, to be 0.2174±0.0092 cm^-1atm^-1 and 0.1327 ±0.0077 cm^-1atm^-1 for self- and N₂ collision broadening, respectively. The broadening coefficients obtained based on IRPS were measured to be ~8% larger than those obtained with IRLIF.     

Water vapor overtones pressure line broadening and shifting measurements

By using a spectrometer having as source a commercial etherostructure Al _x Ga_{1 − x} As diode laser operating in “free-running mode”, line shape parameters of some water vapor ro-vibrational overtones at 820–830 nm have been measured at room temperature. These weak absorption lines have been detected by using the wavelength modulation spectroscopy technique with second-harmonic detection. The broadening and shifting coefficients have been obtained by fitting the collected second-harmonic absorption features while varying the pressure of different foreign gases.     

Theoretical analysis of Resonant Auger Electron Spectra produced by isolated resonances

Summary  Line profiles of Resonant Auger Electron Spectra produced by isolated resonances are analyzed by separating the contributions due to the direct, resonant and interference terms and taking explicitly into account the effects due to the finite bandwidth of the incident radiation. The mean kinetic energy of the emitted electron and the spectral width of the Auger lines are also studied as functions of the parameters characteristic of the incident radiation. The general expressions derived by the theory are applied to the analysis of the lineshapes produced by a specific electronic transition taken from the autoionization spectrum of the CO molecule.     

Persistent spectral hole-burning in a -doped aluminosilicate glass from 8 to 295 K: Study of the burning and refilling kinetics, and of optical dephasing

High-temperature persistent spectral hole-burning (PSHB), up to room temperature, has been observed in a Eu ³⁺ -doped aluminosilicate glass using a high peak-power nanosecond dye laser. Spontaneous refilling as well as thermal cycling measurements show that at least two mechanisms, a fast and a slow one, are involved in our sample. We suggest that the fast or “easy” component may correspond to a non-photochemical local rearrangement of the host or to photoreduction of the Eu ³⁺ ions and that the second one leading to very stable photoproducts may correspond to transfer of an electron over a sizable distance through a several-step process. The mechanisms we suggest agree with light-induced hole refilling measurements. Line broadening mechanisms are discussed and the temperature-dependent part of the homogeneous width and of the spectral shift is interpreted in terms of a two-phonon (Raman) process involving pseudo-local phonons. Received 28 July 1999     

Anharmonic behaviour of BaFCl using Raman scattering

Raman scattering from oriented single crystals of BaFCl was recorded at various temperatures from 20 to 1073 K for the first time. The Raman spectra, corrected for phonon population, were fitted to the sum of four Lorentzian peaks. The peak frequencies and full width at half maximum (FWHM) of the peaks were obtained from the fit. The FWHM is accounted for by cubic and quartic anharmonic processes. The quartic anharmonicity of the mode increases with the mode frequency. The quartic anharmonicity of the fluorine mode is exceptionally high. The peak frequencies decrease linearly with the increasing temperature. Fluorine mode frequencies decrease more than the internal mode frequencies do. The LO-TO splitting of the fluorine modes and that of the internal modes increases with temperature indicating the increase of the ionic bonding character. The results are discussed. Received: 12 May 1997 / Accepted: 25 July 1997     

The origin of disorder in CH 3 HgX (X = Cl, Br and I) crystals investigated by temperature dependent Raman spectroscopy

Methyl-mercury(II) halides CH₃HgX (X = Cl, Br and I) were studied by means of temperature dependent Raman spectroscopy from 10 K to 410 K. In addition to the previously reported soft phonons, new changes in the low frequency spectra were observed at T ≈ 70 K in CH₃HgBr and at T ≈ 100 K in CH₃HgI. The bandwidths of the two internal modes in CH₃HgBr, the CH₃ symmetric stretching band and the C-Hg-Br bending band, rise towards a local maximum at T ≈ 50 K as the temperature is raised from 10 K to 300 K. On the other hand the bandwidths of the two corresponding modes in CH₃HgI crystals monotonously increase with temperature, obeying an Arrhenius law. Besides the three phonon modes present in the Raman spectra of CH₃HgCl at room temperature, the fourth phonon band that has been observed at temperatures below 245 K might correspond to the freezing of methyl librations. The huge bandwidth of the C-Hg-Br bending mode could suggest the presence of additional weak bonding of a mercury atom with bromine atoms from other molecules, thus inducing positional disorder. Received 19 November 1999 and Received in final form 10 November 2000     

Optical study of an untwinned single crystal: ab-plane anisotropy

We report on the ab-plane polarized reflectance of an untwinned single crystal over the frequency range from 80 to (10 meV-4 eV) at temperatures between 10 and 300 K. We find a clear anisotropy in the ab-plane optical conductivity above and below , which is very similar to that formerly published data of (M.A. Quijada et al., Z. Phys. B 94, 255 (1994)). We employ both the one-component and two-component analyses to the optical data, which suggest that the normal-state infrared anisotropy of originates not only from the mass anisotropy, but also from the scattering rate anisotropy. Our results provide evidence that the electronic structures within the plane are anisotropic. In the superconducting state, there is a definite ab-plane anisotropy to the far-infrared absorption. This anisotropy could be due either to anisotropy of the superconducting gap or to anisotropy of the mid-infrared component to the conductivity. We also observe the superconducting condensate is anisotropic: The value of the superconducting penetration depth in the a-direction is slightly smaller than that along the b-axis. Received 16 July 1998     

Investigations on the soft-mode mechanism of the ferroelectric phase transition in

Dielectric and Raman spectroscopic measurements have been performed to investigate the ferroelectric phase transition in . Single crystals were grown by the zone melting method. The frequency dependence of the dielectric permittivity from 1 MHz to 1 GHz has been studied in a temperature range between 265 and 285 K. A Debye like dielectric dispersion was found, showing a critical slowing down around K. Polarized Raman spectra have been taken between 220 and 310 K. Two softening modes have been found, one of A- and another one of B / B g-symmetry. The phase transition mechanism in can be classified as partially order-disorder and partially displacive, confirming former structural results. It resembles strongly that of monoclinic . Received: 7 April 1998 / Revised: 5 June 1998 / Accepted: 16 June 1998     

Line shape analysis of two-colour photoassociation spectra on the example of the Cs ground state

Two-photon photoassociation spectra in a Λ-type excitation scheme are analysed under the systematically varied experimental conditions of frequency detunings and laser intensities. Line shape fits are presented as well as the investigation of intensity and detuning dependent line shifts. From both we determine the attained spectroscopic precision, that is corrected for a systematic line shift due to the thermal distribution of atoms in the trap. An energy correction for this effect is given. Information about the feasibility of generating translationally cold molecules in a well defined rotational and vibrational level by the photoassociation process is derived from the analysis. Received 21 May 2002 Published online 15 October 2002 RID="a" ID="a"Current address e-mail: christian.lisdat@ptb.de RID="b" ID="b"e-mail: pierre.pillet@lac.u-psud.fr