Interpretation of negative birefringence observed in strong-field optical pump-probe experiments: High-order Kerr and plasma grating effects

The analysis of negative birefringence optically induced in major air components (Loriot et al., [1, 2]) is revisited in light of the recently reported plasma grating-induced phase-shift effect predicted for strong field pump-probe experiments (Wahlstrand and Milchberg, [3]). The nonlinear birefrin- gence induced by a short and intense laser pulse in argon is measured by femtosecond time-resolved polarimetry. The experiments are performed with degenerate colors, where the pump and probe beam share the same spectrum, or with two different colors and non-overlapping spectra. The in- terpretation of the experimental results is substantiated using a numerical 3D+1 model accounting for nonlinear…

Field-free molecular alignment of asymmetric top molecules using elliptically polarized laser pulses

International audience; We show theoretically that a short specific elliptically polarized laser pulse driving an asymmetric top molecule can induce postpulse revivals of three-dimensional (3-D) alignment. By choosing the field ellipticity resulting in the best compromise between the alignment of two molecular axes, we demonstrate that efficient 3-D alignment can be achieved at low temperature. In the experiment, the field-free alignment of moderately cool ethylene molecules is probed by using a technique based on the optical Kerr effect. Control of 3-D field-free alignment opens the door to a large range of applications in chemistry as well as in molecular optics.

Quantum control of ground-state rotational coherence in a linear molecule

We present an experimental and theoretical investigation of the quantum control of ground-state rotational coherence in a linear molecule. A sequence of two temporally separated laser pulses creates a rotational superposition state in ${\mathrm{CO}}_{2}$ whose evolution is monitored through a polarization technique. We study the influence of the phase difference between the two pulses. We show that the overlapping of the two wave packets, produced by each pulse, gives rise to quantum interference that affects the orientational anisotropy of the sample. Because of the large number of coherently excited levels, the interference produces well-separated temporal structures, whose magnitude can …

Nonintrusive monitoring and quantitative analysis of strong laser-field-induced impulsive alignment

We report the observation of impulsive alignment of $\mathrm{C}{\mathrm{O}}_{2}$ molecules produced through their interaction with a nonresonant, strong laser pulse. The periodic alignment is monitored using a polarization technique generally employed in optical Kerr effect experiments; the birefringence produced by alignment of the molecular sample is measured with a weak pulse, time-delayed with respect to the alignment pulse. The technique provides a signal proportional to $⟨{\mathrm{cos}}^{2}\phantom{\rule{0.2em}{0ex}}\ensuremath{\theta}⟩\ensuremath{-}\frac{1}{3}$, where $\ensuremath{\theta}$ is the polar angle between the molecular axis and the strong-field polarization axis. Experimen…

Femtosecond time resolved coherent anti-Stokes Raman spectroscopy: Experiment and modelization of speed memory effects on H2-N2 mixtures in the collision regime

194317; With the aim of temperature diagnostic, femtosecond time-resolved CARS (coherent anti-Stokes Raman spectroscopy) is applied to probe H2 in H2-N2 mixtures. In a first part, a Lorentzian profile is used to model the femtosecond CARS response. A difference between the experimental broadening and the expected one is observed in the collision regime. The observed broadening increases strongly in an inhomogeneous way with respect to the perturber concentration. This is of considerable importance for temperature measurements. In a second part, we show that in the collision regime, this inhomogeneous broadening is due to the speed dependence of the collisional parameters and the memory effe…

Dynamical Stark Effect in the nu(2)/nu(4) Vibrational Polyad of SiH(4): Theory and Observation.

We report a theoretical and experimental investigation of the dynamical Stark effect in a tetrahedral molecule, silane (SiH(4)). We use a tetrahedral formalism and Floquet theory to calculate the absorption spectra for the molecule dressed by an intense nonresonant pulsed laser. Experimentally, the dynamical Stark effect is observed for transitions of the nu(2)/nu(4) vibrational polyad of SiH(4) by means of nanosecond diode laser absorption spectroscopy and a Nd:YAG laser excitation. Copyright 2000 Academic Press.

Contrôle de paquets d'ondes rotationnels par impulsions laser ultrabrèves modulées en phase

Une superposition lineaire d'etats rotationnels est produite dans le niveau vibronique de base de la molecule d'azote (Ni) par une impulsion laser ultra-breve non resonnante. Un controle precis de ce paquet d'ondes, a travers la modulation de phase spectrale du champ electrique excitateur, est demontre experimentalement. L'excitation relative entre modes Raman associes a des niveaux de parite donnee est realisee. L'evolution temporelle du paquet d'ondes rotationnel mis en forme est observee par une technique de spectroscopie de polarisation. Les resultats experimentaux sont confortes par une analyse theorique menee dans l'espace des temps et des frequences.

Collisional Relaxation Processes Studied by Coherent Raman Spectroscopy for Major Species Present in Combustions

The effects of collisional relaxation processes on the Q-branch profile of major species present in combustions have been studied by high resolution stimulated Raman spectroscopy. Particular interest has focused on the following collisional systems: N2-N2, O2-O2, CO2-CO2, O2-N2, N2-CO2 and N2-H2O. For each colliding pair, starting from accurate determinations of line broadening coefficients over a wide temperature range, state-to-state rates for rotational energy transfers have been deduced by using various fitting laws. Among these rate laws, special attention has been paid to the temperature dependence of the energy corrected scaling (ECS) law combined with a hybrid exponential-power law …

Field-free molecular alignment for probing collisional relaxation dynamics

International audience; We report the experimental study of field-free molecular alignment in CO2 gas mixtures induced by intense femtosecond laser pulses in the presence of collisional processes. We demonstrate that the alignment signals exhibit specific features due to nontrivial collisional propensity rules that tend to preserve the orientation of the rotational angular momentum of the molecules. The analysis is performed with a quantum approach based on the modeling of rotational J- and M-dependent state-to-state transfer rates. The present work paves the way for strong-field spectroscopy of collisional dynamics.

Higher-order Kerr effect in ultrashort laser pulse propagation and laser filamentation

We discuss the contribution of the higher-order Kerr effect (HOKE) to the propagation of ultrashort laser pulses in several contexts. We show that their consideration is necessary to adequately reproduce experimental data about harmonics generation, propagation in hollow-core fibers, and laser filamentation. In the latter case, our results show that the HOKE play a key role for short pluses and/or long wavelengths, while the plasma contributes more for long pulses and/or short wavelengths.

Measurement of high order Kerr refractive index of major air components: erratum

A clarification is missing concerning the high order Kerr non-linearities deduced from our experimental data published in [Opt. Express 17, 13429-13434 (2009)]. Here, we rectify this omission by making explicit the distinction between cross-Kerr and Kerr effects, and by extrapolating the value of the nonlinear refractive index for the last effect. Since the occurrence of sign inversion in the Kerr effect is not affected, the overall report in [Opt. Express 17, 13429-13434] remains valid.

Collisional line broadening and line shifting in N2-CO2 mixture studied by inverse Raman spectroscopy

Abstract Collisional effects in the Raman Q-branch of N 2 perturbed by CO 2 have been studied by high-resolution stimulated Raman spectroscopy. The Raman spectra recorded in the 0.3–1.0 atm and 295–1000 K pressure and temperature ranges are fitted with a theoretical profile taking into account line broadening, frequency shift and line mixing due to rotational energy transfers. The data at low density are used as basic data for the modeling of rotationally inelastic rates through sets of adjustable parameters. We have used in this study the two main models developed in the last decade and known as modified exponential gap (MEG) and energy corrected sudden (ECS) laws. Experimental spectra rec…

Dunham coefficients of 14N2 from CARS measurements of high vibrational states in a low-pressure discharge

Spectroscopic constants of the X1Σg+ ground state of 14N2 are deduced from CARS spectra recorded in a 4 Torr d.c. N2 glow discharge. Vibrational states up to ν = 14 have been observed but only the 11 lower levels which have a good signal-to-noise ratio have been processed. The Dunham constants that were deduced yield vibrational band centre positions in good agreement with those of Lofthus and Krupenie.

Probing ultrafast thermalization with field-free molecular alignment

International audience; The rotation-translation thermalization of CO2 gas is investigated 500 ps after its preheating by a nonresonant short and intense laser pulse. The temperature of thermalization is optically determined with two additional short laser pulses enabling a field-free molecular alignment process and its probing, respectively. The measurements are performed for various intensities of the preheat pulse, leading to the observation of different temperatures which are in very good agreement with classical molecular dynamics simulations. The results can be regarded as a step towards real-time tracking of ultrafast relaxation pathways in molecular motion.

Study of collisional effects on band shapes of the ν1/2ν2 Fermi dyad in CO2 gas with stimulated Raman spectroscopy. III. Modeling of collisional narrowing and study of vibrational shifting and broadening at high temperature

High resolution stimulated Raman spectra (SRS) of the ν1/2ν2 Fermi dyad of CO2 have been recorded in the 0.4–22. amagat density range at 700 K and in the 0.6–16 amagat density range at 900 K. The data have been successfully analyzed with a theoretical model taking into account both rotational line mixing through the energy corrected sudden‐polynomial (ECS‐P) law for the relaxation matrix and vibrational line broadening γv and line shifting δv. The two vibrational parameters have been accurately determined from fit to the experimental spectra. These new high temperature data together with previous data obtained at 295 and 500 K [B. Lavorel et al., J. Chem. Phys. 93, 2176 (1990); B. Lavorel e…

Measurement and Analysis of the Raman Intensities of 12CD4

0022-2852; The stimulated Raman spectrum of 12CD4 was recorded at high resolution, in the spectral range 1963 to 2260 cm(-1). Intensities of the rovibrational transitions were estimated by fitting the line profiles. The recorded elementary spectrum was 1 cm(-1) wide; all recordings were then intensity calibrated. Afterward, the relative Raman intensities were analyzed by using a polarizability model developed previously [A. Boutahar and M. Loete, Can. J. Phys. 69, 26-35 (1991); J. P. Champion, M. Loete, and G. Pierre, in ''Spectroscopy of the Earth's Atmosphere and Interstellar Molecules'' (K. Narahari Rao and A. Weber, Eds.), pp. 388-397, Academic Press, Boston. 1992]. The investigated reg…

Measurement of high order Kerr refractive index of major air components

International audience; We measure the instantaneous electronic nonlinear refractive index of N2 , O2 , and Ar at room temperature for a 90 fs and 800 nm laser pulse. Measurements are calibrated by post-pulse molecular alignment through a polarization technique. At low intensity, quadratic coefficients n2 are determined. At higher intensities, a strong negative contribution with a higher nonlinearity appears, which leads to an overall negative nonlinear Kerr refractive index in air above 26 TW/cm2 .

Field-free one-dimensional alignment of ethylene molecule

International audience; We report an experimental study of non-adiabatic laser-induced molecular alignment of ethylene (C2H4) using a linearly polarized short laser pulse of moderate intensity. The information about the confinement of the C=C bond axis along the direction of the applied electric field is obtained by measuring the depolarization of a second short pulse of weak intensity interacting with the molecules after they have been exposed to the first pulse. The experimental data are compared with the numerical simulation of the Schr¨odinger equation written for the non-resonant interaction of an asymmetric top rigid rotor with a linearly polarized electric field. The field-free align…

Collisional Broadening of Rotational Lines in the Stimulated Raman Pentad Q-Branch of CD4

Self- and argon-broadening coefficients are reported for a number of Raman Q-branch transitions in the nu(1) and nu(2) + nu(4) bands of (C-12)D4 at room temperature (296 K). The coefficients display a variation with j and with C exp n (symmetry species A, E, F) that is essentially independent of collision partner and which is similar to the j- and C exp n-dependence found in previous measurements of the IR line-broadening coefficients. The rotationally inelastic collision rates previously measured by Foy et al. (1988) for (C-13)D4 (V4 = 0, 1) in collision with (C-13)D4 or Ar account for only a part of the Raman broadening rate, suggesting possibly significant contributions to the linewidths…

Observation of laser-induced continuum structure in the NO molecule

0953-4075; We present experimental results on the modification of a molecular ionization continuum through a laser-induced continuum structure. The effect is demonstrated in nitric oxide where the resonant 2 + 1 multiphoton-ionization process of the X (2)Pi(3/2) electronic ground state is modified by dressing the continuum with the electromagnetically embedded M(2)Sigma(+) Rydberg state. Through selection of a two-photon rovibronic transition via the D electronic state, a single rotational ground state level is excited to the continuum with one laser field. By adding an extra dressing field, a coupling is then established between this three-photon excited ground state level and one of the M…

Characterization of self-phase modulated ultrashort optical pulses by spectral phase interferometry

0740-3224; We present the procedure for measuring self-phase modulation of ultrashort laser pulses focused in gases by use of the spectral phase interferometry for direct electric-field reconstruction (SPIDER) technique. We tested the device, which employs a noncollinear type I frequency mixing scheme, by measuring the phase induced by group-velocity dispersion either in a piece of glass or in the compressor of the laser system. Both results were validated by comparison with the expected values. The phase that resulted from self-phase modulation in H2 gas or atmospheric air was then measured and compared with calculations based on a Gaussian beam assumption. A new estimate of the nonlinear …

Orientation of Polar Molecules by Laser Induced Adiabatic Passage

International audience; We show that two overlapping linearly polarized laser pulses of frequencies ω and its second harmonic 2ω can strongly orient linear polar molecules, by adiabatic passage along dressed states. The resulting robust orientation can be interpreted as a laser-induced localization in the effective double well potential created by the fields, which induces a preliminary molecular alignment. The direction of the orientation can be selected by the relative phase of the fields.

Stimulated Raman and Cars Spectroscopy of ν1 and 2ν2 (A1) Bands of 12CF4

Two experimental coherent Raman techniques, stimulated Raman and coherent anti-Stokes Raman spectroscopy (CARS), were employed to study the Raman spectrum of CF 4 in the 900 cm −1 region. The stimulated Raman and CARS spectra of the ν 1 band of CF 4 were recorded at high resolution. The analysis of these spectra enabled some spectroscopic constants of this band to be refined and higher order constants to be determined for the first time. The first high-resolution CARS spectrum of the 2ν 2 (A 1 ) harmonic band is also presented. The rotational transitions of this band up to J = 40 were assigned and the first set of spectroscopic constants for this sub-level were determined. These results imp…

Optical kerr effect in the strong field regime

The optical Kerr response of hydrogen atom submitted to a strong and short near infrared laser pulse excitation is studied by solving the full 3D time-dependent Schro¨dinger equation. The nonlinear polarization evaluated at the driving field frequency is compared to the canonical expression derived from perturbation theory. A discrepancy between the two models is observed at large intensity affecting the nonlinear propagation of short and intense laser pulses.

Stimulated Raman spectroscopy as the essential tool for studying collisional effects : application to combustion

No abstract available

Using molecular alignment to track ultrafast collisional relaxation

Field-free molecular alignment has been used in order to track the collisional relaxation occurring in a molecular gas. CO${}_{2}$ molecules were initially irradiated by a short linearly polarized laser pulse resulting in the increase of their rotational energy. The evolution of the subsequent ultrafast relaxation process was optically probed after irradiating the sample with a second, weaker, short pulse leading to the alignment of the preheated molecules. Using classical molecular dynamic simulations, we were able to quantitatively reproduce the experimental shapes and amplitudes of the recorded revival transients for a time interval extending from 25 to 500 ps until thermalization of the…

HIGH RESOLUTION STIMULATED RAMAN SPECTROSCOPY WITH A 3 MHz ACCURACY WAVEMETER

Echo-assisted impulsive alignment of room-temperature acetone molecules

International audience; We experimentally and theoretically investigate the field-free alignment of the asymmetric-top acetone molecule. Our study shows that the production of postpulse aligned molecules in a dense sample (0.05-0.2 bar) of room-temperature acetone using a single-pulse excitation can be significantly improved by rotational alignment echoes induced in a two-pulse excitation scheme. We report the observation of fractional echoes that can be used to reveal the nonlinearity of the molecular system. In a proof-of-principle experiment, a pre-aligned sample of acetone is also used for third-harmonic generation. The analysis of the experimental data with numerical simulations based …

Ultrafast buffering by molecular gas

A simple molecular gas sample can be used to achieve ultrafast optical buffering in two-dimensional optical imaging, thus serving as a promising extension of the well-developed liquid-crystal display technology.

L'alignement moléculaire comme une méthode de calibration pour la détermination de probabilité d'ionisation

Par le biais d'une methode originale, nous avons determine experimentalement la probabilite d'ionisation de l'azote (N 2 ) soumis a un champ laser non resonnant et ultracourt (100 fs). La technique de defocalisation croisee mis en oeuvre dans ce travail est sensible a l'alignement moleculaire post-impulsion et a l'ionisation. L'analyse du signal experimental permet d'extraire une probabilite d'ionisation calibree par une mesure d'alignement.

Strong-field molecular ionization: determination of ionization probabilities calibrated with field-free alignment

International audience; We report an original optical method providing the probability of molecular ionization induced by femtosecond laser pulses. The approach consists of exploiting molecular alignment in order to extract reliable information about ionization. The cross defocusing technique implemented for this purpose reveals a sensitivity with respect to post-pulse alignment, as well as to free electron density induced by the ultra-short laser pulse. The analysis of the resulting signal gives thus access to absolute single-ionization probabilities calibrated through the degree of alignment provided that free electrons are mainly produced from single-ionization. The relevance of the meth…

Scaling laws for inelastic collision processes in diatomic molecules

International audience

Accurate spectroscopic constants of nitrogen determined from stimulated Raman spectra of the fundamental and first hot bands

Nitrogen spectra of the Q-branch of the fundamental and the first hot bands were recorde with a high-resolution stimulated Raman spectrometer at atmospheric pressure and ca. 1300 K. The absolute frequencies of the Raman lines were measured with high accuracy, leading to a refinement of spectroscopic constants. A temperature estimation was also performed from the Raman intensities.

Orientation and Alignment Echoes

We present one of the simplest classical systems featuring the echo phenomenon---a collection of randomly oriented free rotors with dispersed rotational velocities. Following excitation by a pair of time-delayed impulsive kicks, the mean orientation or alignment of the ensemble exhibits multiple echoes and fractional echoes. We elucidate the mechanism of the echo formation by the kick-induced filamentation of phase space, and provide the first experimental demonstration of classical alignment echoes in a thermal gas of ${\mathrm{CO}}_{2}$ molecules excited by a pair of femtosecond laser pulses.

Collisional shifting and broadening coefficients for the rovibrational anisotropic S(J) lines of nitrogen studied by inverse Raman spectroscopy

0377-0486; Line shifting and broadening coefficients of the anisotropic S(J) lines (v = 0, J --> v = 1, J + 2) of the nitrogen molecule were measured at room temperature using high-resolution stimulated Raman spectroscopy. A rotational quantum number dependence of the S(J) line shifts was observed. In order to avoid an asymmetry of experimental origin, a suitable theoretical profile was fitted to the experimental lineshapes. This study allows the testing of the theoretical methods for calculating the line broadening coefficients in anisotropic Raman scattering, which have already been used in the analysis of infrared absorption data. The behaviour of the modified sum rule and the RPA (rando…

Temperature measurement in gas mixtures by femtosecond Raman-induced polarization spectroscopy

The potential of femtosecond Raman-induced polarization spectroscopy (RIPS) for the simultaneous determination of temperature and concentrations was investigated. These measurements were related to the rotational time response of the molecular gas mixture, which was measured as a function of the pump-probe time delay. The change of the polarizability anisotropy with respect to the vibrational levels was taken into account. The results of temperature measurements in pure CO2 showed good agreement with the values obtained by a thermocouple. The RIPS technique was also applied to a CO2-N2 gas mixture to determine simultaneously temperatures and concentrations at temperatures up to 600 K. The a…

Collisional shifting and broadening coefficients for the rovibrational anisotropic lines of the ν1/2ν2 fermi dyad in CO2 gas studied by stimulated Raman spectroscopy

High-resolution stimulated Raman spectroscopy was applied to the study of collisional broadening and shifting for rovibrational anisotropic Raman lines of the Fermi dyad of molecular carbon dioxide. The O(J) lines of the ν1 band and the S(J) lines of the 2ν2 band were recorded at 295 K. The pressure-induced line shifts were obtained and compared with the overall shift of the high-density Raman Q-branch. A rotational quantum number dependence of the rovibrational line broadening coefficients was observed. The experimental line broadening coefficients were used in order to check the ability of two theoretical methods (random phase approximation and sum rule) for calculating the line broadenin…

Determination of temperature by stimulated raman scattering of molecular nitrogen, oxygen, and carbon dioxide

We have determined the temperature from SRS spectra of N2-N2, N2-CO2, O2-O2, and CO2-CO2 recorded in wide pressure and temperature ranges. The fitting procedure takes simultaneously into account the Dicke effect and motional narrowing. We have quantified the accuracy of the MEG and ECS-P models for rotational relaxation. The temperature extracted from each model is compared with thermocouple measurements. The influence of vibrational broadening and shifting is discussed in detail.

Field-free two-direction alignment alternation of linear molecules by elliptic laser pulses

We show that a linear molecule subjected to a short specific elliptically polarized laser field yields postpulse revivals exhibiting alignment alternatively located along the orthogonal axis and the major axis of the ellipse. The effect is experimentally demonstrated by measuring the optical Kerr effect along two different axes. The conditions ensuring an optimal field-free alternation of high alignments along both directions are derived.

Rotational collisional line broadening at high temperatures in the N2 fundamental Q-branch studied with stimulated Raman spectroscopy

Self broadened N 2 Q-branch spectra are measured by high resolution stimulated Raman spectroscopy in the pressure region 0.25-1.9 atm. and in the temperature range 295-1310 K. Non additivity of the Q(J) components due to line overlap arising in the highest pressure range explored is carefully taken into account. Excellent fit of the whole spectra is thus obtained for each pressure with linearly density-dependent line widths. Semi-classical calculations of the line-broadening coefficients lead to consistent values with all the measured ones. These calculations are extended to higher J values and to higher temperatures (up to 2500 K). At last, a simple phenomenological model based on a polyno…

Measurement of laser-induced alignment of molecules by cross defocusing

0146-9592; The field-free alignment of CO2 produced in response to the excitation of a molecule by a high-intensity femtosecond pump pulse is measured with a simple coronography-like technique. The technique is based on the defocusing of a time-delayed probe pulse produced by the spatial distribution of aligned molecules. In the intensity regime explored here, the technique is shown to give valuable information about dynamic alignment. With the help of simulations, the degree of alignment is extracted from the data. (C) 2005 Optical Society of America.

Self-focusing in Terbium Gallium Garnet using Z-scan

International audience; When illuminated near its resonance with an Ar ion laser beam (lambda=488 nm), laser induced thermal self-focusing is observed in Terbium Gallium Garnet. The crystal exhibits a strong intensity dependent refractive index change Dn. The Z-scan technique is used to study the beam waist change due to Dn. The refractive index is found to be well described by a quadratic spatial distribution model. Both the sign and the distribution coefficient of Dn are determined.

Wavelength dependence of multiphoton ionization of xenon

We have studied the multiphoton ionization of xenon atoms by $160\phantom{\rule{0.3em}{0ex}}\mathrm{fs}$ pulses at intensities of $5\ifmmode\times\else\texttimes\fi{}{10}^{12}$ and $1.3\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{0.3em}{0ex}}\mathrm{W}∕{\mathrm{cm}}^{2}$ and present photoelectron kinetic energy and angular distribution spectra measured with a photoelectron imaging spectrometer. A noncollinear optical parametric amplifier allows us to tune the wavelength of the laser pulse over a range between 500 and $700\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. Resonant and nonresonant processes as well as channel switching effects have been observed in this intensity and wavel…

Shaping of a ground state rotational wavepacket by frequency-chirped pulses

0953-4075; A coherent rotational superposition state is produced in the ground vibronic level of N2 through the interaction of the molecule with the electric field vector of a nonresonant laser pulse. This rotational wavepacket is shaped with a linear frequency chirp of the laser field. The structural shape of the rotational coherences shows a strong dependence with the frequency-chirp amplitude. A comparison with a theoretical model allows the interpretation of the observed effects in terms of dephasing of the wavepacket induced by the laser phase distortion. Application of the presented results to the phase characterization of short XUV pulses is suggested.

Field-free molecular alignment for measuring ionization probability

International audience; We have shown in a recent letter (Loriot et al 2006 Opt. Lett. 31 2897) the possibility of determining the ionization probability of linear molecules by using an all-optical technique that takes advantage of post-pulse molecular alignment. To that end, we have implemented a ‘cross-defocusing' technique producing a signal sensitive to both alignment and ionization. The analysis of the signal provides a quantitative measurement of the ionization probability calibrated with molecular alignment. In the present work, the method is discussed in more detail and applied to the measurement of the ionization probability of N2 as well as to the determination of the ionization r…

Optical rotary power at the resonance of the Terbium 7F6→5D4 line in Terbium Gallium Garnet

Abstract The Tb 3+ absorption line 7 F 6 → 5 D 4 of the Terbium Gallium Garnet crystal is excited with an Argon ion laser. The Verdet's constant has been determined and reported against 1/ λ 2 , showing no significant resonant behaviour at absorption resonance. The utility and the constraints of the crystal at this particular resonant wavelength are pointed out.

Optically Probed Laser-Induced Field-Free Molecular Alignment

Molecular alignment induced by laser fields has been investigated in research laboratories for over two decades. It led to a better understanding of the fundamental processes at play in the interaction of strong laser fields with molecules, and also provided significant contributions to the fields of high harmonic generation, laser spectroscopy, and laser filamentation. In this chapter, we discuss molecular alignment produced under field-free conditions, as resulting from the interaction of a laser pulse of duration shorter than the rotational period of the molecule. The experimental results presented will be confined to the optically probed alignment of linear as well as asymmetric top mol…

Laser spatial profile effects in measurements of impulsive molecular alignment

0953-4075; We use a non-intrusive technique based on a polarization scheme to probe the periodic alignment of the CO2 and N2 molecules induced by a strong laser pulse linearly polarized. A weak probe field experiences the birefringence resulting from the alignment of the molecules. By comparing the probe depolarization signal with the numerical simulation of the time-dependent Schrödinger equation, it is possible to quantify the alignment of the molecular sample. The modelling takes into account the spatial profile of the pump intensity. It allows from the alignment signal to determine the onset of saturation due to ionization, despite the intrinsic saturation of the alignment arising for a…

Pressure broadening, shift, and interference effect for a multiplet line in the rovibrational anisotropic stimulated raman spectrum of molecular oxygen

0022-2852; High-resolution stimulated inverse Raman spectroscopy has been applied to the study of collisional broadening, shifting, and line mixing for the O-o(J, N = 5) triplet line of the fundamental vibrational band of molecular oxygen. Accurate line broadening coefficients for the individual J components within the triplet have been measured for the first time and show a significant J dependence. The line broadening coefficients are larger than those previously obtained for unresolved pure rotational Raman lines. The additional broadening is expected to result from electronic spin relaxation. The pressure-induced line shift has been obtained for this Line and compared to the value obtai…

Controlling ground-state rotational dynamics of molecules by shaped femtosecond laser pulses

We report controlled excitation of ground-state rotational wave packet by pulse-shaping technique. The experiment is conducted in nitrogen $({\mathrm{N}}_{2})$ at room temperature and atmospheric pressure. A femtosecond laser pulse produces rotational coherences in the vibronic ground state of ${\mathrm{N}}_{2}$ through an impulsive Raman process. The laser pulse is tailored using a spatial light modulator producing spectral phase modulation. Periodic phase steps are applied in order to control the excitation of specific rotational Raman transitions. The outcome is the modification of the relative excitation between odd and even rotational states which allows the control of the symmetry and…

Transition from plasma-driven to Kerr-driven laser filamentation.

While filaments are generally interpreted as a dynamic balance between Kerr focusing and plasma defocusing, the role of the higher-order Kerr effect (HOKE) is actively debated as a potentially dominant defocusing contribution to filament stabilization. In a pump-probe experiment supported by numerical simulations, we demonstrate the transition between two distinct filamentation regimes at 800 nm. For long pulses (1.2 ps), the plasma substantially contributes to filamentation, while this contribution vanishes for short pulses (70 fs). These results confirm the occurrence, in adequate conditions, of filamentation driven by the HOKE rather than by plasma.

Enhancement of sensitivity in high-resolution stimulated Raman spectroscopy of gases: Applicaion to the 2ν2 (1285 cm−1) band of CO2

The application of a multiple-pass gas cell to quasi-cw stimulated Raman scattering is demonstrated to be a powerful method for significantly increasing the sensitivity. As a consequence, such a device offers the possibility of working in the 0.1–1 Torr pressure range for weak bands. As a striking example, experimental results are given for the 2ν2 band of CO2 at 1285 cm−1. The band is almost completely resolved with a very good signal-to-noise ratio. The Raman frequencies and the collisional broadening coefficients are determined as a function of quantum number J. Moreover, the possibility of auto-stimulated Raman effect on CO2 at moderate pressure via the sharp ν1 band (1388 cm−1) is demo…

Long-transient conoscopic pattern technique

0038-1098; Recent results on laser induced anisotropy in terbium gallium garnet are extended to the dynamic regime. We observed that the characteristic conoscopic pattern formation time presents a quadratic dependence on the beam size. The observed pattern intensity is accounted for by a simple analytical formula. The transient refractive index change due to thermal stress in the terbium gallium garnet is determined. (C) 1999 Elsevier Science Ltd. All rights reserved.

Line mixing in the stimulated Raman spectrum of the ν1 band of SiH4 at 0.4–1.0 bar

The stimulated Raman spectrum of the ν1 band of SiH4 has been recorded at 0.4 and 1.0 bar pressures and room temperature. Line mixing of the fine structure components of this spectrum was taken into account in a calculated profile by considering coupling between the main transitions and using a simple model (strong collision model, SCM) for the relaxation matrix.

High-resolution non-linear Raman spectroscopy in gases

The resolution in the Raman spectra of gases has been greatly improved by the development of the different methods of non-linear Raman scattering. When two laser beams, one of which has a tunable frequency, are focused in a sample, a stimulated Raman process occurs as soon as the frequency difference between the two lasers is equal to a Raman-active rovibrational or rotational transition frequency. The Raman resonance can be detected in different ways: by coherent anti-Stokes Raman scattering (CARS) or the corresponding Stokes process (CSRS), by a gain in one of the beams (stimulated Raman gain spectroscopy, SRGS) or a loss in the other (inverse Raman spectroscopy, IRS), or even by detectio…

High Resolution Coherent Raman Spectroscopy: Studies of Molecular Structures

One of the main advantages of the non-linear coherent Raman techniques is the high resolution that can be achieved in rovibrational spectroscopy. Typically an instrumental function of the order of several thousandths of a wavenumber is routinely achieved in SRS or CARS experiments. Since the first recording of the stimulated Raman spectrum of 12CH4 in 1978 [1], numerous studies of molecules have been performed [2–8]. We have built a stimulated Raman experiment in Dijon in which particular attention has been paid to the frequency measurement of the Raman lines [9]. We will describe the application of our experiment to a wide variety of molecules over the last few years: linear molecules, sph…

Postpulse molecular alignment measured by a weak field polarization technique

We report a direct nonintrusive observation of alignment and planar delocalization of ${\mathrm{C}\mathrm{O}}_{2}$ after an intense linearly polarized femtosecond laser pulse excitation. The effects are measured by a polarization technique involving a perturbative probe that itself does not induce appreciable alignment. We show that this technique allows one to measure a signal proportional to $⟨{cos}^{2}\ensuremath{\theta}⟩\ensuremath{-}1/3$, with $\ensuremath{\theta}$ the angle between the molecular axis and the laser polarization. Simulations that support this analysis allow one to characterize the experimentally observed alignment and planar delocalization quantitatively.

Temporal phase control of bound-bound and bound-free two-photon transitions in NO with two time-delayed cross-polarized pulses

0953-4075; Temporal phase control over the multi-photoionization of NO is investigated experimentally The coherent excitation of the molecular system is achieved by a sequence of two phase-related non-Fourier-transform-limited laser pulses delivered by a nanosecond dye laser, The phase-locked pulses are produced by making use of an actively stabilized interferometer with a tunable pathlength difference. As the coherence time of the laser is comparable with the inhomogenous dephasing time of the medium, the measurements are performed with temporally overlapped pulses. In order to avoid the modulation of the ionic signal coming from optical interference, the linear polarizations of the two pu…

Line coupling in Anisotropic Raman Branches

Direct connection between collisional Raman cross sections and state‐to‐state rotational ones permits, within the sudden approximation, to evidence drastic decouplings from isotropic to anisotropic lines. These decouplings are consistent with the results obtained by using the strong collision model. Convenient energy corrections to the sudden approximation are used for N2 to calculate the resulting effects on the isotropic and anisotropic Q‐branch profiles in a large density range (several hundred bars). The comparison of the calculations with experimental coherent anti‐Stokes Raman scattering (CARS) and stimulated Raman (SRS) spectra of nitrogen exhibits a good agreement. Such effects coul…

Spectral dependence of purely-Kerr driven filamentation in air and argon

5 pags, 4 figs.-- PACS number(s): 42.65.Jx, 42.65.Tg, 78.20.Ci. -- Publisher error corrected 27 September 2010, Erratum Phys. Rev. A 82, 039905 (2010): https://doi.org/10.1103/PhysRevA.82.033826

Concentration measurements in molecular gas mixtures with a two-pump pulse femtosecond polarization spectroscopy technique

0021-9606; Recently, we have demonstrated the ability of the Raman-induced polarization spectroscopy (RIPS) technique to accurately determine concentration or polarizability anisotropy ratio in low-pressure binary molecular mixtures [E. Hertz, B. Lavorel, O. Faucher, and R. Chaux, J. Chem. Phys. 113, 6629 (2000)]. It has been also pointed out that macroscopic interference, occurring when two revivals associated to different molecules time overlap, can be used to achieve measurements with picosecond time resolution. The applicability of the technique is intrinsically limited to a concentration range where the signals of both molecules are of the same magnitude. In this paper, a two-pump puls…

Field-free molecular alignment of CO2 mixtures in presence of collisional relaxation

The present work explores the extension of the concept of short-pulse-induced alignment to dissipative environments within quantum mechanical density matrix formalism (Liouville equation) from the weak to the strong field regime. This is illustrated within the example of the CO2 molecule in mixture with Ar and He, at room temperature, for which a steep decrease of the alignment is observed at moderate pressure because of the collisional relaxation. The field-free alignment is measured by a polarization technique where the degree of alignment is monitored in the time domain by measuring the resulting transient birefringence with a probe pulse Raman induced polarization spectroscopy (RIPS) Co…

Harmonic Generation and Nonlinear Propagation: When Secondary Radiations Have Primary Consequences

In this Letter, it is experimentally and theoretically shown that weak odd harmonics generated during the propagation of an infrared ultrashort ultraintense pulse unexpectedly modify the nonlinear properties of the medium and lead to a strong modification of the propagation dynamics. This result is in contrast with all current state-of-the-art propagation model predictions, in which secondary radiations, such as third harmonic, are expected to have a negligible action upon the fundamental pulse propagation. By analyzing full three-dimensional ab initio quantum calculations describing the microscopic atomic optical response, we have identified a fundamental mechanism resulting from interfere…

Laser-induced field-free alignment of the OCS molecule

We investigate the dynamical alignment of jet-cooled OCS molecules induced by a short laser pulse. The alignment is measured through the orientational contribution of the optical Kerr effect using a second weak laser pulse as a probe. Maximum alignment is observed at conditions close to saturation of ionization. The results are analysed with a quantum mechanical model solving for the rotational dynamics.

Pulse trains produced by phase-modulation of ultrashort optical pulses: tailoring and characterization

1094-4087; In this paper, creation of pulse doublets and pulse trains by spectral phase modulation of ultrashort optical pulses is investigated. Pulse doublets with specific features are generated through step-like and triangular spectral phase modulation, whereas sequences of pulses with controllable delay and amplitude are produced via sinusoidal phase modulations. A temporal analysis of this type of tailored pulses is exposed and a complete characterization with the SPIDER technique (Spectral Phase Interferometry for Direct Electric-field Reconstruction) is presented. (C) 2004 Optical Society of America.

Observation of laser-induced field-free permanent planar alignment of molecules

International audience; Permanent planar alignment of gas-phase linear molecules is achieved by a pair of delayed perpendicularly polarized short laser pulses. The experiment is performed in a supersonic jet, ensuring a relatively high number density of molecules with moderately low rotational temperature. The effect is optically probed on a femtosecond time scale by the use of a third short pulse, enabling a time-resolved birefringence detection performed successively in two perpendicular planes of the laboratory frame. The technique allows for an unambiguous estimation of the molecular planar delocalization produced within the polarization plane of the pulse pair after the turn-off of the…

General approach to spatiotemporal modulational instability processes

International audience; In this article, we derive the general exact solution of the modulation instability gain. The solution described here is valid for 1-D, 2-D, and 3-D cases considering any temporal response function of the medium and with possible higher order Kerr nonlinearities. In particular, we show that the gain induced by modulation instability is initial condition dependent, while the usual calculations do not lead to such a dependence. Applications for current and high-interest nonlinear propagation problems, such as 1-D optical fiber propagation with delayed Raman response and 2-D filamentation in gases, are investigated in detail. More specifically, we demonstrate that the 2-D …

Study of interacting bands of silane: Analysis of infrared and Raman spectra

Abstract The ν 1 ν 3 interacting bands of natural silane have been studied by Fourier transform spectroscopy and stimulated Raman spectroscopy, respectively, in the regions 2040–2320 and 2180–2187 cm−1. These data combined with available microwave observations have been analyzed using a reduced effective Hamiltonian developed through the fifth order for 28SiH4 and through the fourth order for 29SiH4 and 30SiH4. The observed infrared and Raman transitions have been very well reproduced with a standard deviation of about 0.0004 cm−1 for 28SiH4. Some anomalies in the Hamiltonian expansion have been found, but they did not perturb the analysis.

Higher-order Kerr effects improve quantitative modelling of harmonics generation and laser filamentation

The consideration of the higher-order Kerr effect (HOKE) drastically improves the quantitative agreement between measured and simulated harmonic yield as well as intensity and electron density in laser filaments generated by pulses below a few hundreds of fs. In longer pulses, the plasma defocusing plays a much more important role.

Field-free molecular alignment in presence of collisional relaxations

Determination of concentrations in ternary and quaternary molecular gas mixtures using femtosecond Raman spectroscopy

Measurements of concentrations in gas mixtures of three and four molecular components are presented. They rely on a femtosecond time-resolved pump–probe technique based on Raman-induced polarization spectroscopy. The rotational time response of the molecular gas mixture is measured as a function of the pump–probe time delay. No selective frequency tunability is needed as the molecular rotational spectra are excited within the laser bandwidth. The results obtained from experiments performed at room temperature in N2O–CO2–N2 and N2O–CO2–O2–N2 mixtures are presented and the accuracy of the method is discussed. Copyright © 2002 John Wiley & Sons, Ltd.

Application of time-resolved spectroscopy to concentration measurements in gas mixtures

1296-2147; Concentration measurements using femtosecond Raman Induced Polarization Spectroscopy (RIPS) are performed in binary gas mixtures CO2-N2 and CO2-N2O at room temperature. The principle of these measurements is based on the nonlinear rotational time response of each molecular component of the mixture, The general form of this molecular response is a series of periodic transients with a period related to the rotational constant Be The relative strength of the individual responses allows an accurate determination of the concentration. Two techniques are presented using either two pulses (one pump and one probe) or three pulses (two pumps and one probe). (C) 2001 Academie des sciences/…

A Rotational Thermalization Model for the Calculation of Collisionally Narrowed Isotropic Raman-Scattering Spectra - Application to the Srs-N2 Q-Branch

Abstract A model for the calculation of collisionally narrowed isotropic. Raman scattering spectra is proposed. In this model, the rotational transition probabilities are calculated within the strong collision approximation, allowing the rotational energy transfer rates to be expressed in terms of the sole individual Q( J ) line broadening coefficients. These transfer rates satisfy both detailed balance principle and unitarity of the scattering matrix in contrast with most of the previous approaches. Under further approximation concerning the rotational distribution of the collisional frequency, simpler expressions for transfer rates are deduced, which do not satisfy necessarily both unitar…

Control of field-free molecular alignment by phase-shaped laser pulses

We report an experimental study of the control of molecular alignment of ${\mathrm{N}}_{2}$ by use of spectrally modulated pulses at an intensity regime below the intrinsic saturation of the alignment. By manipulating the relative timing of the alignment revival pattern arising from the even subset of the thermal ensemble as compared to the odd subset, we demonstrate that the angular distribution of the aligned molecule can be converted into planar delocalization at specific times. We also show that the angular focusing of the molecular axis can be switched off by applying a specific bipulse.

Analysis of femtosecond Raman-induced polarization spectroscopy (RIPS) in N2 and CO2 by fitting and scaling laws

Raman-induced polarization spectroscopy (RIPS) experiments were conducted at room temperature and pressures below 2 atm in pure N2 and CO2. Both homodyne and optically heterodyne detection were used. Calculations of the signal as a function of the pump–probe delay were performed taking into account the pulse duration of the laser, the rotational dependence of the dephasing rates and the small instantaneous electronic Kerr effect. The observed decay and shape of the rotational quantum beats are in good agreement with the calculations. Several sets of linewidth coefficients corresponding to the diagonal part of the collisional–rotational relaxation matrix were used. This matrix was choosen am…

Field-free molecular alignment induced by elliptically polarized laser pulses: Noninvasive three-dimensional characterization

International audience; An investigation of field-free molecular alignment produced by elliptically polarized laser pulses is reported. Experiments are conducted in CO2 at room temperature. A noninvasive all-optical technique, based on the cross defocusing of a probe pulse, is used to measure the alignment along two orthogonal directions which is sufficient to provide a three-dimensional characterization. The field-free molecular alignment produced by a laser of elliptical polarization is in good agreement in terms of amplitude and shape with theoretical predictions. It turns out to be almost equivalent to the superposition of the effects that one would obtain with two individual cross-pola…

Femtosecond Raman Spectroscopy of C2H4 and CH4 molecules

Optical gratings induced by field-free alignment of molecules

We analyze the alignment of molecules generated by a pair of crossed ultra-short pump pulses of different polarizations by a technique based on the induced time-dependent gratings. Parallel polarizations yield an intensity grating, while perpendicular polarizations induce a polarization grating. We show that both configurations can be interpreted at moderate intensity as an alignment induced by a single polarized pump pulse. The advantage of the perpendicular polarizations is to give a signal of alignment that is free from the plasma contribution. Experiments on femtosecond transient gratings with aligned molecules were performed in CO2 at room temperature in a static cell and at 30 K in a …

Optimization of field-free molecular alignment by phase-shaped laser pulses

We theoretically demonstrate the optimization of field-free molecular alignment by phase-shaped femtosecond laser pulses. The effect is assessed in ${\mathrm{O}}_{2}$ at $T=60\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ under realistic conditions of intensity and pulse shaping. The spectral laser phase is sampled through 128 control parameters and a self-learning evolutionary algorithm combined with a nonperturbative regime calculation is used in order to design the specific phase that maximizes the degree of alignment. The postpulse molecular alignment appears significantly enhanced compared to a Fourier-transform-limited pulse of same energy. The analysis of the target state reveals that the so…

High rate concentration measurement of molecular gas mixtures using a spatial detection technique

International audience; Concentration measurement in molecular gas mixtures using a snapshot spatial imaging technique is reported. The approach consists of measuring the birefringence of the molecular sample when field-free alignment takes place, each molecular component producing a signal with an amplitude depending on the molecular density. The concentration measurement is obtained on a single-shot basis by probing the time-varying birefringence through femtosecond time-resolved optical polarigraphy (FTOP). The relevance of the method is assessed in air.

Spectroscopie Raman Anti-Stokes Cohérente femtoseconde (DRASC – fs) : expériences et modélisation dans le cas du mélange H2 – N2 à basse pression

Dans l'objectif du diagnostic de la temperature dans les milieux en combustion, la Diffusion Raman Anti-Stokes Coherente resolue en temps (DRASC - fs) est utilisee pour sonder H 2 dans les melanges H 2 -N 2 a basse pression. Le dispositif DRASC mis en place est decrit en detail. Un nouveau modele de la reponse DRASC temporelle, prenant en compte tous les effets collisionnels specifiques a l'hydrogene (effets dits « de vitesse ») est presentee, ainsi que la comparaison avec l'experience, l'accord se revelant tres satisfaisant.

Higher-order Kerr terms allow ionization-free filamentation in gases.

We show that higher-order nonlinear indices ($n_4$, $n_6$, $n_8$, $n_{10}$) provide the main defocusing contribution to self-channeling of ultrashort laser pulses in air and Argon at 800 nm, in contrast with the previously accepted mechanism of filamentation where plasma was considered as the dominant defocusing process. Their consideration allows to reproduce experimentally observed intensities and plasma densities in self-guided filaments.

Snapshot imaging of postpulse transient molecular alignment revivals

Laser induced field-free alignment of linear molecules is investigated by using a single-shot spatial imaging technique. The measurements are achieved by femtosecond time-resolved optical polarigraphy (FTOP). Individual alignment revivals recorded at high resolution in ${\text{CO}}_{2}$, as well as simultaneous observation of several alignment revivals produced within the rotational period of the ${\text{O}}_{2}$ molecule are reported. The data are analyzed with a theoretical model describing the alignment experienced by each molecule standing within the interaction region observed by the detector. The temporal dynamics, intensity dependence, and degree of alignment are measured and compare…

Speed-memory effects in H2-N2 mixtures studied by CARS femtosecond. Experiments and modelization from the collisional to the Doppler regime

High-field quantum calculation reveals time-dependent negative Kerr contribution

The exact quantum time-dependent optical response of hydrogen under strong field near infrared excitation is investigated and compared to the perturbative model widely used for describing the effective atomic polarization induced by intense laser fields. By solving the full 3D time-dependent Schr\"{o}dinger equation, we exhibit a supplementary, quasi-instantaneous defocusing contribution missing in the weak-field model of polarization. We show that this effect is far from being negligible in particular when closures of ionization channels occur and stems from the interaction of electrons with their parent ions. It provides an interpretation to higher-order Kerr effect recently observed in v…

Femtosecond Raman time-resolved molecular spectroscopy

International audience; The applicability of several femtosecond time resolved non-linear coherent techniques such as Raman induced polarization spectroscopy (RIPS), degenerate four-wave mixing (DFWM) and coherent anti-Stokes Raman spectroscopy (CARS) for molecular spectroscopy is presented. All methods rely on the initial coherent excitation of molecular states producing wavepackets, whose time evolution is then measured. In the case of RIPS and DFWM only pure rotational transitions are involved, whereas in CARS vibrational states can be excited. First the methodology of concentration and temperature measurements using RIPS in gas mixtures involving N2, CO2, O2, and N2O is shown. In additi…

Revised Analysis of the Structure of the v1 Band of Methane

Abstract The CARS spectrum of the v 1 band of 12 CH 4 at a pressure of 14 mbar was recorded using cw excitation in the cavity of a ring argon ion laser. The analysis of the intensity profile of the obarred spectrum led to the detection of inconsistencies with the hitherto proposed calculated positions of transitions with J = 7 to J = 10 and to a relocation of the corresponding lines.

An experimental investigation of the nonlinear refractive index (n2) of carbon disulfide and toluene by spectral shearing interferometry and z-scan techniques

International audience; The recently proposed spectral shear interferometry and the well-known z-scan techniques were employed for the determination of the nonlinear refractive index n2 of CS2, toluene and fused silica. The determined n2 values by both techniques were found to be in very good agreement. In addition, the role of the repetition rate of the laser is also investigated revealing its importance for the correct determination of both the size and the sign of the nonlinearity.

Methane line parameters in HITRAN

Abstract Two editions of the methane line parameters (line positions, intensities and broadening coefficients) available from HITRAN in 2000 and 2001 are described. In both versions, the spectral interval covered was the same (from 0.01 to 6184.5 cm −1 ), but the database increased from 48,033 transitions in 2000 to 211,465 lines in 2001 because weaker transitions of 12 CH 4 and new bands of 13 CH 4 and CH3D were included. The newer list became available in 2001 in the “Update” section of HITRAN. The sources of information are described, and the prospects for future improvements are discussed.

Suppression of plasma contribution in femtosecond degenerate four-wave mixing (fs-DFWM) at high intensity

Femtosecond degenerate four-wave mixing (fs-DFWM) experiments in CO2 exhibit a strong background due to plasma produced at high intensity (≥20 TW/cm2), when significant molecular alignment is likely to arise. This perturbing phenomenon renders the measurements of alignment very difficult. It is shown that the plasma contribution can be avoided by employing perpendicular polarizations for the two pump pulses. The effect is explained on the basis of the different diffraction angles between signals produced by molecular alignment and plasma. Copyright © 2007 John Wiley & Sons, Ltd.

High-Resolution Stimulated Raman Spectroscopy of Methane 13CD4 in the Pentad Region

Abstract We present the first Raman spectrum of 13CD4 recorded at room temperature in the pentad region by inverse Raman spectroscopy, thus including the ν1 (A1), 2ν2 (A1), 2ν4 (A1), and ν2 + ν4(F1 + F2) Q branches. It is noteworthy that the overtone bands 2ν2 and 2ν4 are observed for the first time in a methane-like molecule by a coherent Raman process. The wide frequency range investigated, covering 45 cm−1 in three parts, contains more than 300 lines with uncertainty less than 10−3 cm−1 in most cases. These Raman data are combined with high-resolution infrared data in a weighted least-squares fit of the vibration-rotation constants of the pentad, thanks to a relevant partially reduced ef…

Femtosecond Raman time-resolved molecular spectroscopy

Abstract The applicability of several femtosecond time resolved non-linear coherent techniques such as Raman induced polarization spectroscopy (RIPS), degenerate four-wave mixing (DFWM) and coherent anti-Stokes Raman spectroscopy (CARS) for molecular spectroscopy is presented. All methods rely on the initial coherent excitation of molecular states producing wavepackets, whose time evolution is then measured. In the case of RIPS and DFWM only pure rotational transitions are involved, whereas in CARS vibrational states can be excited. First the methodology of concentration and temperature measurements using RIPS in gas mixtures involving N2, CO2, O2, and N2O is shown. In addition some applica…

Optical Imaging of Coherent Molecular Rotors

International audience; Short laser pulses are widely used for controlling molecular rotational degrees of freedom and inducing molecular alignment, orientation, unidirectional rotation and other types of coherent rotational motion. To follow the ultra-fast rotational dynamics in real time, several techniques for producing molecular movies have been proposed based on the Coulomb explosion of rotating molecules, or recovering molecular orientation from the angular distribution of high-harmonics. The present work offers and demonstrates a novel non-destructive optical method for direct visualization and recording of movies of coherent rotational dynamics in a molecular gas. The technique is b…

Ultrafast collisional dissipation of symmetric-top molecules probed by rotational alignment echoes

We experimentally and theoretically investigate the ultrafast collisional dynamics of a symmetric-top molecule (${\mathrm{C}}_{2}{\mathrm{H}}_{6}$) in pure gas and mixtures with He at high density by employing the rotational alignment echo created by a pair of time-delayed intense laser kicks. The decrease of the amplitude of the echo when increasing the delay between the two laser pulses, reflecting the collisional relaxation of the system, is measured by probing the transient birefringence induced in the medium. The theoretical predictions, carried using purely classical molecular dynamics simulations, reproduce well the observed features, as demonstrated previously for a linear molecule.…

Ab InitioCalculations and High-Resolution Spectroscopy of the Bending Pentad of SiH2D2in the 10–16 μm Region

Abstract The SiH 2 D 2 asymmetric top has nine vibrational modes, five of them forming a pentad strongly perturbed by Coriolis interactions. High-level ab initio calculations of SiH 2 D 2 have been performed which yield numerous spectroscopic parameters related to the harmonic and anharmonic force fields. The bending pentad comprising ν 4 (A 1 ), ν 7 (B 1 ), ν 5 (A 2 ), ν 9 (B 2 ), and ν 3 (A 1 ) has been studied by high-resolution Fourier transform spectroscopy; the region 600–1050 cm −1 has been investigated with a resolution of ca. 4 × 10 −3 cm −1 . Raman BOXCARS spectroscopy has been used for the infrared inactive ν 5 band. The Raman apparatus function was 0.0054 cm −1 . Assignments of …

Rotational echoes as a tool for investigating ultrafast collisional dynamics of molecules

We show that recently discovered rotational echoes of molecules provide an efficient tool for studying collisional molecular dynamics in high-pressure gases. Our study demonstrates that rotational echoes enable the observation of extremely fast collisional dissipation, at timescales of the order of a few picoseconds, and possibly shorter. The decay of the rotational alignment echoes in ${\mathrm{CO}}_{2}$ gas and ${\mathrm{CO}}_{2}\text{\ensuremath{-}}\mathrm{He}$ mixture up to 50 bar was studied experimentally, delivering collision rates that are in good agreement with the theoretical expectations. The suggested measurement protocol may be used in other high-density media, and potentially …

Measurments of collisional line widths in the stimulated Raman Q-branch of the ν1 band of silane

Self-broadened widths of 28SiH4 in the ν1Q-branch have been measured at room temperature (295 K) using high-resolution stimulated Raman Spectroscopy. These collisional widths have been obtained by fitting a super-position of Voigt profiles to the experimental spectra in the pressure range 28–154 Torr. No evidence for line mixing within the tetrahedral components of a Q(J) line has been found. The line broadening coefficients for J up to 13 depend weakly on the rotational quantum number. The mean value is 103.7 × 10−3 cm−1 atm−1.

Dissipation of post-pulse laser-induced alignment of CO2through collisions with Ar

In this paper, laser-induced field-free alignment of CO2 in mixtures with Ar is investigated under dissipative conditions (up to 15 bars) at room temperature. The degree of alignment is temporally monitored by a polarization spectroscopy technique, where a weak probe pulse measures the transient birefringence resulting from the alignment. The data are analyzed with a quantum mechanical density matrix formalism using properly J-dependent and M-dependent state-to-state transfer rates, which was previously successfully tested on pure CO2 and CO2–He mixtures. The same consistency is obtained between experiments and calculations, in particular the decay times of both the transient revivals and t…

Computational investigation and experimental considerations for the classical implementation of a full adder on SO2 by optical pump-probe schemes

International audience; Following the scheme recently proposed by Remacle and Levine Phys. Rev. A 73, 033820 2006 , we investigate the concrete implementation of a classical full adder on two electronic states X˜ 1A1 and C ˜ 1B2 of the SO2 molecule by optical pump-probe laser pulses using intuitive and counterintuitive stimulated Raman adiabatic passage excitation schemes. The resources needed for providing the inputs and reading out are discussed, as well as the conditions for achieving robustness in both the intuitive and counterintuitive pump-dump sequences. The fidelity of the scheme is analyzed with respect to experimental noise and two kinds of perturbations: The coupling to the neigh…

Vibrational and rotational collisional relaxation in CO2–Ar and CO2–He mixtures studied by stimulated Raman-infrared double resonance

0021-9606; The collisional relaxation among vibrational levels of the Fermi dyad of CO2 mixed with Ar and He (10% CO2, 90% rare gas) has been studied at room temperature with a double resonance experiment. Stimulated Raman effect from the ground state achieved the pumping process with a Nd:YAG laser and a pulse amplified dye laser. After pumping the v(1) or 2v(2)(Sigma(+)g) level, a cw CO2 laser was used to probe either the depopulation rates of the pumped levels (vibrationally or rotationally resolved) or the energy transfer rates to neighboring states. The vibrational energy relaxation has been studied from experimental depopulation of v(1) and population of 2v(2) levels through a five-le…

A POWERFUL TOOL TO STUDY COLLISIONAL PHENOMENA AND FOR COMBUSTION APPLICATIONS : THE HIGH RESOLUTION STIMULATED RAMAN SPECTROSCOPY

Electrostrictive limit in the detection of weak stimulated Raman signals in gases

0377-0486; It is shown experimentally that, in stimulated Raman spectroscopy, electrostriction induced by the pump laser gives rise to a non-resonant signal detected on the probe laser. This phenomenon limits the detectivity of the experiment. A qualitative interpretation is given. (C) 1997 by John Wiley & Sons, Ltd.

High-resolution photoacoustic Raman spectroscopy of gases

A high-resolution photoacoustic Raman spectroscopy experiment is described. The resolution achieved by using two single-mode pulsed lasers is about 0.0054 cm −1 (full width at half maximum intensity). The experiment was tested first on the v 1 /2v 2 bands of CO 2 and gave an increase of at least about one order of magnitude in the signal-to-noise ratio with respect to stimulated Raman spectroscopy at low pressure (ca. 10 Torr ≃ 1.3 kPa). The sensitivity is also demonstrated by the study of the weak hot band v 1 +v 2 −v 2 of CO 2 . In both cases, the experimental line shape is well reproduced by taking into account Doppler and collisional effects. A comparison with CARS spectra was also made

Preliminary analysis of the pentad of 13CH4 from Raman and infrared spectra

Abstract Preliminary results on the simultaneous analysis of infrared and Raman data of 13 CH 4 in the 3-μm region ( ν 1 , ν 3 , 2 ν 2 , ν 2 + ν 4 , and 2 ν 4 ) are presented. The infrared spectrum of 13 CH 4 (90% enriched) has been recorded with the Fourier transform spectrometer at Kitt Peak National Observatory. Line positions have been measured with a relative accuracy of 0.0001 cm −1 (for well-isolated lines) using 0.0118-cm −1 resolution spectra. In order to compensate for the lack of infrared information about low J transitions of vibrational bands forbidden in infrared, two spectra of the ν 1 ( A 1 ) and 2 ν 2 ( A 1 ) Q branches have been recorded in Dijon by inverse Raman spectrosc…

Polarization shaping for unidirectional rotational motion of molecules.

Control of the orientation of the angular momentum of linear molecules is demonstrated by means of laser polarization shaping. For this purpose, we combine two orthogonally polarized and partially time-overlapped femtosecond laser pulses so as to produce a spinning linear polarization which in turn induces unidirectional rotation of N2 molecules. The evolution of the rotational response is probed by a third laser beam that can be either linearly or circularly polarized. The physical observable is the frequency shift imparted to the probe beam as a manifestation of the angular Doppler effect. Our experimental results are confirmed by theoretical computations, which allow one to gain a deep p…

Optical Diagnostics with Ultrafast and Strong Field Raman Techniques

In this chapter, we will discuss some coherent techniques, namely Raman Induced Polarization Spectroscopy (RIPS) and femtosecond Coherent Raman Anti-Stokes Spectroscopy (fs-CARS). We will demonstrate their ability to be used as non-invasive optical diagnostic tools for temperature, density, or concentration measurements, as well as a means of testing collision induced energy transfer models (in a low field regime), and studying the so-called inhomogeneous lineshape effects that are particularly enhanced in the case of hydrogen. We will also show how molecular alignment achieved in a strong field regime can provide additional information about collisional relaxation processes. In all cases, …

Controlling molecular alignment rephasing through interference of Raman-induced rotational coherence

0021-9606; Quantum control over molecular alignment rephasing is experimentally investigated in gaseous CO2. The control process is achieved by illuminating the medium with a pair of pump-pulses separated in time by approximately an integer value of T0=1/8B(0), where B(0) is the rotational constant. Through a Raman-type process, each pulse alone produces rotational coherence leading to a periodic orientational anisotropy. It is the combination of the two pulses that yields to quantum interference, resulting in a modification of this anisotropy probed by a third delayed pulse. The effect is accurately analyzed for different time delays between the two pulses. A theoretical analysis supplies …

Rotational Raman spectroscopy of ethylene using a femtosecond time-resolved pump-probe technique.

154309; Femtosecond Raman-induced polarization spectroscopy (RIPS) was conducted at low pressure (250 mb at 295 K and 400 mb at 373 K) in ethylene. The temporal signal, resulting from the beating between pure rotational coherences, was measured with a heterodyne detection. The temporal traces were converted to the frequency domain using a Fourier transformation and then analyzed thanks to the D2hTDS software (http://www.u-bourgogne.fr/LPUB/shTDS.html) dedicated to X2Y4 molecules with D2h symmetry. The effective Hamiltonian was expanded up to order 2, allowing the determination of five parameters with an rms of 0.017 cm(-1). Special care was taken in the precise modeling of intensities, taki…

A direct study of the vibrational bending effect in line mixing: The hot degenerate 1110 ← 0110 transition of CO2

Abstract The study of the isotropiv Raman Q -branch of a hot band Π ← Π allows one to establish a direct connection between the vibration-rotation angular momentum coupling and the resulting spectra. Due to the l -doubling, the Q -branch is split into two subbranches characterized by either even or odd rotational quantum number j . The vibrational bending reduces the rotational transfer rates inside each of these subbranches by a factor of about two and induces an inter-subbranch coupling. The expected propensity rule towards conservation of the parity index for high rotational levels is well observed. Calculated spectra are in excellent agreement with CARS experiments for the v 1 + v 2 ← v…

Femtosecond polarization spectroscopy in molecular gas mixtures: Macroscopic interference and concentration measurements

0021-9606; Raman-induced polarization spectroscopy (RIPS) experiments combined with homodyne detection have been conducted with a femtosecond laser at room temperature and low pressure (p < 2 atm) in CO2-N2 mixtures as well as in air (O2-N2 mixtures). Each molecule of the mixture produces its own time-dependent signal, measured as a series of recurring transients. Macroscopic interference is observed when transients of both molecules overlap in the time domain. This interference leads to a large modification of the signal, which is well reproduced by calculations. The total signal recorded in CO2-N2 or O2-N2 mixtures of known concentration is analyzed in order to measure the polarizability …

Molecular alignment echoes probe collision-induced rotational-speed changes

International audience; We show that the decays with pressure of the rotational alignment echoes induced in N 2 O-He gas mixtures by two ultrashort laser pulses with various delays show detailed information about collision-induced changes of the rotational speed of the molecules. Measurements and classical calculations consistently demonstrate that collisions reduce the echo amplitude all the more efficiently when the echo appears late. We quantitatively explain this behavior by the filamentation of the classical rotational phase space induced by the first pulse and the narrowing of the filaments with time. The above mentioned variation of the echo decay then reflects the ability of collisi…