CARS spectroscopy of molecules and clusters in supersonic jets

Supersonic molecular beams of D₂, CH₄, NH₃, and C₂H₄ are investigated in the expansion region employing collinear coherent anti-Stokes Raman spectroscopy (CARS). The analysis of rotationally resolved CARS spectra allows the determination of temperatures in the beam. The rotational relaxation as a function of stagnation pressure and separation from the nozzle is studied by recording theQ branch for D₂ and the ₃ R andS branches for CH₄. Rotational temperatures for NH₃ are determined by investigating the complete ₃ band. At strong stagnation conditions broad structures arise which can be attributed to the formation of NH₃ clusters. For C₂H₄ the ₅ band with resolved rotational structure is reported. Again, at larger distances from the nozzle, broad structures are observed. They are assigned to the ₁ and ₅ vibrations in the C₂H₄ cluster.     

The binding of alkali atoms to the surfaces of liquid helium and hydrogen

Alkali atoms have been shown previously to have only unstable binding states inside liquid⁴He. We calculate the equilibrium configurations and binding energies of single alkali atoms near the liquid-vapor interface of⁴He and³He. A simple interface model is used to predict the surface deformation due to the presence of the atoms. A more realistic density functional model yields somewhat higher energies in the case of⁴He. For all alkali atoms, we find the surface binding energies to be around 10 to 20 K. A similar analysis with atom-H₂ interactions finds that alkali atoms tend to submerge into liquid H₂, with the exception of Li.     

Sublevel spectroscopy of alkali atoms in superfluid helium

We report the results of optical pumping and optical detection of magnetic resonance of alkali atoms (Cs and Rb) in superfluid helium. The magnetic resonances between the ground-state Zeeman sublevels and hyperfine levels are observed through monitoring theD ₁ fluorescence by means of the optical-rf double resonance technique. Although the ground stateg values in superfluid helium are the same as in vacuum within the experimental error, the hyperfine constant of the ground state of the Cs atom in superfluid helium is found to be slightly larger than in vacuum. Coherent transient spectroscopy is also performed.     

Size-selected, supported clusters: the interaction of carbon monoxide with nickel clusters

We report on the size-dependent chemical reactivity of nickel clusters with up to 30 atoms. Monodispersed Ni₃₀ clusters show a higher reactivity for CO dissociation than Ni₁₁ and Ni₂₀. Under our experimental conditions the smallest nickel clusters (Ni_x, x<4) produce nickelcarbonyl complexes. These results demonstrate that such small clusters are unique for catalytic reactions not only due to their high surface-to-volume ratio but also essentially because of the distinctive properties of different cluster sizes. In addition thermal desorption spectroscopy of CO shows that on average four molecules are weakly adsorbed per Ni₁₁ at saturation coverage. Using an isotopic mixture of ¹²CO and ¹³CO, infrared spectroscopy reveals the existence of a vibrational coupling interaction between the four COs. A semi-classical model of interacting dipoles is applied to correlate the observed vibrational frequency shifts with the arrangement of the COs on the cluster. This simple analysis favors a three-dimensional structure for the deposited clusters. Received: 23 March 1998/Accepted: 25 August 1998     

Charge transfer between alkali cluster ions and atoms in the 1 to 10 keV collisional energy range

The cross-sections for collisional charge transfer between singly charged free clusters M _n ⁺ (M = Li, Na; n=1...50) and atomic targets A (cesium, potassium) have been measured as a function of collisional relative velocity in laboratory energy range 1–10 keV. For each cluster size, the experimental values of the charge transfer cross-section are fitted with an universal parametric curve with two independent parameters and v_m, the maximum cross-section and the corresponding velocity. For small size clusters (), the characteristic parameters show strong variations with the number of atoms in the cluster. Abrupt dips observed for n=10 and n=22 are attributed to electronic properties. Charge transfer patterns observed for various collisional systems present similarities, which appear more sensitive to cluster quantum size effects than to collision energy defects. In their whole, the and v_m parameters show differences in both their size evolution and their absolute values discussed in term of projectile and target electronic structures. Received 13 April 2000 and Received in final form 29 June 2000     

Plasmon resonances observed in light scattered by large alkali clusters

Received: 14 October 1996/Revised version: 15 January 1997     

Computer study of acetylene and ethane adsorption by disperse water medium

Adsorption of acetylene and ethane molecules by water clusters has been investigated by the molecular dynamics method at T=233 K. With the help of determination of statistical weights the cluster systems are created. In the frequency range of 0?ω?1000 cm⁻¹ the integral absorption coefficient of IR-radiation increases after the adsorption of acetylene or ethane molecules by the ultra disperse water system. The dissipation power of IR-radiation by cluster systems increases if C₂H₂ molecules are adsorbed, and it reduces in the case of C₂H₆ molecules' adsorption.     

Degenerate four-wave mixing in nitrogen dioxide: Application to combustion diagnostics

Single shot degenerate four wave mixing (DFWM) images of the distribution of nitrogen dioxide (NO₂) doped into a propane/air flame at concentrations of the order of 7000 ppm have been obtained. These images indicate the relative concentration of NO₂ in different parts of the flame with an estimated spatial resolution of 150 m.Initial experiments were performed using NO₂ in a glass cell with nitrogen buffer gas. DFWM signals were generated using both the frequency doubled output of a pulsed ND:YAG laser and the tunable blue output of an excimer pumped dye laser. The signal was investigated as a function of laser power, NO₂ concentration and buffer gas pressure. In addition, spectra of NO₂ in the region 450 to 480 nm were obtained.Signals were then sought in both a cold air/NO₂ gas flow and an ignited mixture of propane and air seeded with NO₂, using a DFWM imaging geometry. The resulting images from the flame demonstrate the disappearance of the NO₂ molecules in the flame interaction zone.This work was done when previously employed by AEA Technology at Harwell     

Spectroscopy of the a3Σu + state and the coupling to the X1Σg + state of K2

We report on high resolution Fourier-transform spectroscopy of fluorescence to the a³Σ_u ⁺ state induced by two-photon or two-step excitation from the X¹Σ_g ⁺ state to the 2³Π_g state in the molecule K₂. These spectroscopic data are combined with recent results of Feshbach resonances and two-color photoassociation spectra for deriving the potential curves of X¹Σ_g ⁺ and a³Σ_u ⁺ up to the asymptote. The precise relative position of the triplet levels with respect to the singlet levels was achieved by including the excitation energies from the X¹Σ_g ⁺ state to the 2³Π_g state and the frequencies of the fluorescence down to the a³Σ_u ⁺ state in the simultaneous fit of both potentials. The derived precise potential curves allow for reliable modeling of cold collisions of pairs of potassium atoms in their ²S ground state. Electronic supplementary material Supplementary Online Material     

New observation and analysis of the E(4)Σ state in NaLi

Polarization labeling spectroscopy is applied to study the excited E(4)¹Σ⁺ state of NaLi in the energy range 25 850-27 750 cm⁻¹ above the bottom of the ground state. The potential curve of the E state is constructed using the Inverted Perturbation Approach method.     

Spectroscopy of calcium deposited on large argon clusters

Spectroscopic experiments have been performed, providing emission and excitation spectra of calcium atoms trapped on argon clusters of average size 2 000. The two experimental spectra fall in the vicinity of the calcium resonance line ¹P ₁ → ¹S₀ at 422.9 nm. The excitation spectrum consists in two bands located on each side of the resonance line of the free calcium. In addition, Monte Carlo calculations, coupled to Diatomics-In-Molecule potentials are employed to simulate the absorption spectrum of a single calcium atom in the environment of a large argon cluster of average size 300. The theoretical absorption spectrum confirms the existence of two bands, and shows that these bands are characteristic of a calcium atom located at the surface of the argon cluster and correspond to the excited 4p orbital of calcium either perpendicular or parallel to the cluster surface. The precise comparison between the shape of the absorption spectrum and that of the fluorescence excitation spectrum shows different intensity ratios. This could suggest the existence of a non adiabatic energy transfer that quenches partly the fluorescence of trapped calcium. Another explanation, although less likely, could be a substantial dependence of the calcium oscillator strength according to the alignment of the calcium excited orbital with respect to the cluster surface. The emission spectrum always shows a band in the red of the resonance line which is assigned to the emission of calcium remaining trapped on the cluster. When exciting the blue band of the excitation spectrum, the emission spectrum shows a second, weak, component that is assigned to calcium atoms ejected from the argon clusters, indicating a competition between ejection and solvation. Received 7 May 2002 Published online 1st October 2002 RID="a" ID="a"e-mail: jmm@drecam.saclay.cea.fr RID="b" ID="b"URA 2453 du CNRS RID="c" ID="c"UMR 5626 du CNRS     

Photoluminescence of 1,3-Diphenyl-1H-pyrazolo[3,4-b]quinoline and its derivatives: Experiment and quantum chemical simulations

The optical absorption and photoluminescent spectra are studied in recently synthesized diphenyl pyrazoloquinolines (DPPQ): 1,3-diphenyl-1H-pyrazolo[3,4-b] quinoline and its 6-vinyl, 6-N,N-diphenyl, 6-methyl, 6-fluoro, 6-bromo and 6-chloro derivatives. The photoemission spectra are recorded in organic solvents of different polarity and found to be highly solvatochromic. The measured spectra are compared with the quantum chemical calculations performed by means of the semiempirical methods (AM1 or PM3) in combination with the equilibrium molecular conformation (EMC) in vacuo (T = 0 K, Γ = 0.12 eV) or MD simulations (T = 300 K). The broadening of absorption and emission bands and their red-shift with increasing of temperature may be well reproduced by MD simulations. The Stokes shift of the photoluminescent spectra is obtained by including vibrational modes into the emission equation. The quantum chemical method AM1 in combination with MD simulations gives in most cases the best agreement with the experimental data. By comparing the emission spectra of 6-N,N-diphenyl-DPPQ with other DPPQ-derivatives one concludes that the molecular fragment diphenyl-amin [(C₆H₅)₂N-] is likely subjected to strong conformational changes in solvents. The large difference between the excited- and state-dipole moments indicates on a strong electron transfer effect being common for all DPPQ derivatives.     

Dynamics of Na clusters in picosecond laser pulses

We investigate the electronic and ionic dynamics of Na clusters under the influence of a laser pulse in the range 100 femtoseconds to picoseconds. The dynamics is described by means of the time-dependent local-density approximation coupled to ionic molecular dynamics (TDLDA-MD). Variation of pulse length allows us to explore the time scales of ionic motion in a manner similar to pump and probe experiments. Resonant enhancement of electron emission serves as a measure for the time scale of Coulomb explosion. Received: 3 July 2001 / Published online: 10 October 2001     

Coherent raman spectroscopy of nitrogen molecules and clusters in supersonic jets

Coherent Stokes and anti-Stokes Raman scattering CSRS and CARS have been employed to study the spectroscopy of nitrogen molecules and clusters in the expansion of a supersonic jet. In the vibrational spectrum, at strong stagnation conditions, an intense redshifted peak is observed which can be assigned to the intramolecular vibrations in large N₂ clusters having adopted the -phase structure. Another weak feature is assigned to nitrogen clusters in the -phase. In the rotational region of the spectrum only monomer features have been observed. The failing to observe librational motions is consistent with the finding that the nitrogen clusters are predominantly in the orientationally unordered -phase. The low rotational temperature suggests supercooling of the -phase.     

DFT studies of ionic vibrations in Na clusters

We use time-dependent density functional theory coupled to molecular dynamics for ionic motion to compute the spectra of ionic vibrations in small Na clusters. Comparison with results from the distance dependent tight-binding approach shows good agreement between these two very different methods. We discuss the evolution of the spectra with cluster size and charge and the impact of ionic vibrations on the optical response. Received 23 July 2001 / Received in final form 5 July 2002 Published online 8 October 2002 RID="a" ID="a"e-mail: suraud@irsamc.ups-tlse.fr     

Optical absorption of 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its derivatives

Paper deals with the experimental investigations and quantum chemical calculations of the absorption spectra of newly synthesized 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its 6-Vinyl, 6-N,N-Diphenyl, 6-Methyl, 6-Fluoro, 6-Bromo, and 6-Chloro derivatives. The calculations are performed by means of the semiempirical quantum chemical methods AM1 or PM3 combined with: (a) equilibrium molecular conformation (EMC) in vacuo; (b) the molecular conformation model considering a dynamical rotation of phenyl rings only (T = 300 K); and (c) the most general model of the conformational molecular dynamics (MD) at T = 300 K. It is shown that the phenyl dynamics appears to be not important in the spectral position of absorption thresholds as well as in a broadening of most absorbtion bands. On the other hand, the MD simulations reproduce a broadening of the absorbtion spectra as well as the electron-vibronic coupling leading to a red-shift of absorption bands with increasing of temperature. The conformational MD model in combination with the quantum chemical AM1 method gives in most cases the best agreement with the experimental data, namely in the sense of spectral positions and width of the absorption bands including first oscillators (absorption thresholds).