Infrared light on molecule-molecule and molecule-surface collisions

By analyzing measured infrared absorption of pure CH4 gas under both "free" (large sample cell) and "confined" (inside the pores of a silica xerogel sample) conditions we give a demonstration that molecule-molecule and molecule-surface collisions lead to very different propensity rules for rotational-state changes. Whereas the efficiency of collisions to change the rotational state (observed through the broadening of the absorption lines) decreases with increasing rotational quantum number J for CH4-CH4 interactions, CH4-surface collisions lead to J-independent linewidths. In the former case, some (weak) collisions are inefficient whereas, in the latter case, a single collision is sufficient to remove the molecule from its initial rotational level. Furthermore, although some gas-phase collisions leave J unchanged and only modify the angular momentum orientation and/or symmetry of the level (as observed through the spectral effects of line mixing), this is not the case for the molecule-surface collisions since they always change J (in the studied J=0-14 range).

Quantitative laboratory spectroscopy of atmospheric trace gases

info:eu-repo/semantics/published

Foreword: Molecular complexes in our atmosphere and beyond

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12C2H2-Ar van der Waals complex

New theoretical and experimental results on the acetylene-Ar van der Waals complex are presented and the literature is reviewed. New ab initio calculations at the MP2 level were performed using large basis sets with diffuse functions and taking into account the basis set superposition error. It was found that the structure of acetylene is not significantly altered by the complexation and that its vibrational frequencies are only slightly lowered. Finally, it was observed that the calculated properties of the complex (structure, vibrational spectrum, bond dissociation energy) are not sensitive to the structure imposed on acetylene. Experimentally, acetylene-Ar was produced in a supersonic expansion under experimental conditions corresponding to 9 K rotational temperature. Thanks to the performances of CW-CRDS detection, the Ka = 0 ← 1, 1 ← 0, and 2 ← 1 sub- bands of the v1 + v3 band could be recorded and resolved and most of their lines assigned. Upper-state rotational constants were fitted, however not including the upper Ka = 2 state, which shows K-doubling the opposite of the expected. The Lorentzian width of most line profiles sets the mean lifetime to some 7.5 ns. Local perturbations affecting line positions and/or line widths are demonstrated. Additional series of lines tentatively attributed to acetylene-Ar are discussed.© 2009 American Chemical Society.

First High-Resolution Analysis of the Absorption Spectrum of Propane in the 6.7-7.5 μm Spectral Region

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Equilibrium structure of the hydrogen bonded dimer H2O ⋯ HF

The equilibrium structure of the hydrogen bonded complex H2O HF has been calculated ab initio using the CCSD(T) method with basis sets up to sextuple- quality with diffuse functions and taking into account the basis set superposition error correction. The calculations carried out confirm the importance of diffuse functions and of counterpoise correction to obtain an accurate geometry. The most important point is that the basis set convergence is extremely slow and, for this reason an accurate ab initio structure requires a very large basis set. Nevertheless, the ab initio structure is significantly different from the experimental r0 and rm structures. Analysis of the basis set convergence and of the approximations used for the determination of the experimental structures indicates that the ab initio structure is expected to be more reliable.

Special issue devoted to molecular complexes in our atmosphere and beyond

SCOPUS: ed.j

Absolute line intensities for formic acid and dissociation constant of the dimer

Absolute line intensities in the v6 and v8 interacting bands of trans-HCOOH, observed near 1105.4 and 1033.5 cm -1, respectively, and the dissociation constant of the formic acid dimer (HCOOH)2 have been measured using Fourier transform spectroscopy at a resolution of 0.002 cm-1. Eleven spectra of formic acid, at 296.0(5) K and pressures ranging from 14.28(25) to 314.0(24) Pa, have been recorded between 600 and 1900 cm-1 with an absorption path length of 19.7(2) cm. 437 integrated absorption coefficients have been measured for 72 lines in the v6 band. Analysis of the pressure dependence yielded the dissociation constant of the formic acid dimer, k p=361(45) Pa, and the absolute intensity of the 72 lines of HCOOH. The accuracy of these results was carefully estimated. The absolute intensities of four lines of the weak v8 band were also measured. Using an appropriate theory, the integrated intensity of the v6 and v 8 bands was determined to be 3.47 × 1017 and 4.68 × 10-19 cm-1/(molecule cm-1) respectively, at 296 K. Both the dissociation constant and integrated intensities were compared to earlier measurements. © 2007 American Institute of Physics.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 microns

This paper was selected by the editors of the Journal of Chemical Physics as one of the few of the many notable JCP articles published in 2009 that present ground-breaking research

Vibration-rotation pattern in acetylene: Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 µm

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Regulation of the alpha-fetoprotein promoter: Ku binding and DNA spatial conformation

This work shows that the proximal promoter of the mouse Afp gene contains a Ku binding site and that Ku binding is associated with down-regulation of the transcriptional activity of the Afp promoter. The Ku binding site is located in a segment able to adopt a peculiar structured form, probably a hairpin structure. Interestingly, the structured form eliminates the binding sites of the positive transcription factor HNF1. Furthermore, a DNAse hypersensitive site is detected in footprinting experiments done with extracts of AFP non-expressing hepatoma cells. These observations suggest that the structured form is stabilised by Ku and is associated with extinction of the gene in AFP non-expressing hepatic cells.

Rotational analysis of the v6 band in furan (C4H4O)

SCOPUS: no.j

New high-resolution analysis of the ν7 and ν9 fundamental bands of trans-formic acid by IR Fourier transform and millimeterwave spectroscopies

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Science objectives and performances of NOMAD, a spectrometer suite for the ExoMars TGO mission

The NOMAD spectrometer suite on the ExoMars Trace Gas Orbiter will map the composition and distribution of Mars atmospheric trace species in unprecedented detail, fulfilling many of the scientific objectives of the joint ESA-Roscosmos ExoMars Trace Gas Orbiter mission. The instrument is a combination of three channels, covering a spectral range from the UV to the IR, and can perform solar occultation, nadir and limb observations. In this paper, we present the science objectives of the instrument and how these objectives have influenced the design of the channels. We also discuss the expected performance of the instrument in terms of coverage and detection sensitivity.

Supercontinuum generation in air-silica microstructured fibers with nanosecond and femtosecond pulse pumping

We study the generation of supercontinua in air-silica microstructured fibers by both nanosecond and femtosecond pulse excitation. In the nanosecond experiments, a 300-nm broadband visible continuum was generated in a 1.8-m length of fiber pumped at 532 nm by 0.8-ns pulses from a frequency-doubled passively Q-switched Nd:YAG microchip laser. At this wavelength, the dominant mode excited under the conditions of continuum generation is the LP 11 mode, and, with nanosecond pumping, self-phase modulation is negligible and the continuum generation is dominated by the interplay of Raman and parametric effects. The spectral extent of the continuum is well explained by calculations of the parametric gain curves for four-wave mixing about the zero-dispersion wavelength of the LP11 mode. In the femtosecond experiments, an 800-nm broad-band visible and near-infrared continuum has been generated in a 1-m length of fiber pumped at 780 nm by 100-fs pulses from a Kerr-lens model-locked Ti:sapphire laser. At this wavelength, excitation and continuum generation occur in the LP01 mode, and the spectral width of the observed continuum is shown to be consistent with the phase-matching bandwidth for parametric processes calculated for this fiber mode. In addition, numerical simulations based on an extended nonlinear Schrödinger equation were used to model supercontinuum generation in the femtosecond regime, with the simulation results reproducing the major features of the experimentally observed spectrum. © 2002 Optical Society of America.