Collision-induced Raman scattering by rare-gas atoms: The isotropic spectrum of Ne–Ne and its mean polarizability

We report the room-temperature isotropic collision-induced light scattering spectrum of Ne–Ne over a wide interval of Raman shifts, and we compare it with the only available experimentalspectrum for that system as well as with spectra calculated quantum-mechanically with the employ of advanced ab initio -computed data for the incremental mean polarizability. Thespectral range previously limited to 170 cm−1 is now extended to 485 cm−1 allowing us to successfully solve the inverse-scattering problem toward an analytic model for the meanpolarizability that perfectly matches our measurements. We also report the depolarization ratio of the scattering process, lingering over the usefulness of this property for more stringent checks between the various polarizability models

Anisotropic collision-induced Raman scattering by the Kr:Xe gas mixture

We report anisotropic collision-induced Raman scattering intensities by the Kr–Xe atomic pair recorded in a gas mixture of Kr and Xe at room temperature. We compare them to quantum-mechanical calculations on the basis of modern incremental polarizability models of either ab initio post-Hartree–Fock or density functional theory methods

Collision-induced Raman scattering and the peculiar case of neon: Anisotropic spectrum, anisotropy, and the inverse scattering problem

Owing in part to the p orbitals of its filled L shell, neon has repeatedly come on stage for its peculiar properties. In the context of collision-induced Raman spectroscopy, in particular, we have shown, in a brief report published a few years ago [M. Chrysos et al., Phys. Rev. A 80, 054701 (2009)], that the room-temperature anisotropic Raman lineshape of Ne–Ne exhibits, in the far wing of the spectrum, a peculiar structure with an aspect other than a smooth wing (on a logarithmic plot) which contrasts with any of the existing studies, and whose explanation lies in the distinct way in which overlap and exchange interactions interfere with the classical electrostatic ones in making the polarizability anisotropy, α ∥ − α ⊥. Here, we delve deeper into that study by reporting data for that spectrum up to 450 cm−1 and for even- and odd-order spectral moments up to M 6, as well as quantum lineshapes, generated from SCF, CCSD, and CCSD(T) models for α ∥ − α ⊥, which are critically compared with the experiment. On account of the knowledge of the spectrum over the augmented frequency domain, we show how the inverse scattering problem can be tackled both effectively and economically, and we report an analytic function for the anisotropy whose quantum lineshape faithfully reproduces our observations

Experimental observation of the ν2_{2}+4ν3_{3} bands of HD16^{16}O and HD18^{18}O between 14975 and 15275 cm−1^{-1}

The ν$_{2}$+4ν$_{3}$ combination bands of HD$^{16}$O and HD$^{18}$O were measured using Fourier transform-incoherent broadband cavity-enhanced absorption spectroscopy (FT-IBBCEAS) with a spectral resolution of 0.08 cm$^{-1}$. The ro-vibrational lines of these bands were assigned through comparison with ab-initio molecular lines from the Tomsk variational calculation database (http://spectra.iao.ru/). For HD$^{18}$O and HD$^{16}$O in total 114 and 141 strong lines were assigned in the region between 14975.3 cm$^{-1}$ and 15243.3 cm$^{-1}$ and between 14998.5 cm$^{-1}$ and 15274.7 cm$^{-1}$, respectively. While the very satisfactory agreement of line intensities was used for line assignments, a systematic average discrepancy of ~0.305 cm$^{-1}$ in line positions was identified between the measured lines of HD$^{18}$O and the theoretically predicted lines from the Tomsk database. Similarly for HD$^{16}$O, an approximate wavenumber difference of ~0.361 cm$^{-1}$ was observed. The wavenumber accuracy of the Fourier transform cavity enhanced absorption spectrometer was confirmed on basis of concurrently measured H$_{2}$$^{16}$O spectra in the region between 15254.2 cm$^{-1}$ and 15376.9 cm$^{-1}$ and corroborated the systematic shifts of the ab initio data. A few lines of the ν$_{1}$+4ν$_{2}$+2ν$_{3}$ bands of HD$^{16}$O and HD$^{18}$O were also identified. The data are compared and discussed on basis of existing literature data

Anisotropic collision-induced Raman scattering by Ne-Ne: Evidence for a nonsmooth spectral wing

We report the anisotropic collision-induced scattering (CIS) spectrum of two neon atoms at room temperature. The covered spectral range hitherto restricted to 170 cm−1 is here tripled. Both our measurements and quantum-mechanical calculations obtained on the basis of large-scale ab initio anisotropy representations reveal a well-defined saddle-shaped wing. This peculiar structure is experimental evidence of a binary CIS line shape with an aspect other than a smooth wing in a logarithmic plot. Equally interesting is the fact that this feature has been predicted (though only qualitatively) by the simple semiempirical model long ago reported by Meinander, Tabisz and Zoppi J. Chem. Phys. 84 3005 (1986), but no emphasis had at that time been placed on the aspect of the wing of the model spectrum probably due to the lack of high-frequency experimental data

Long optical cavities for open-path monitoring of atmospheric trace gases and aerosol extinction

An incoherent broadband cavity-enhanced absorption spectroscopy setup employing a 20 m long optical cavity is described for sensitive in situ measurements of light extinction between 630 and 690 nm. The setup was installed at the SAPHIR atmospheric simulation chamber during an intercomparison of instruments for nitrate (NO3) radical detection. The long cavity was stable for the entire duration of the two week campaign. A detection limit of similar to 2 pptv for NO3 in an acquisition time of 5 s was established during that time. In addition to monitoring NO3, nitrogen dioxide (NO2) concentrations were simultaneously retrieved and compared against concurrent measurements by a chemiluminescence detector. Some results from the campaign are presented to demonstrate the performance of the instrument in an atmosphere containing water vapor and inorganic aerosol. The spectral analysis of NO3 and NO2, the concentration dependence of the water absorption cross sections, and the retrieval of aerosol extinction are discussed. The first deployment of the setup in the field is also briefly described

Synthesis of a square-planar rhodium alkylidene N-heterocyclic carbene complex and its reactivity toward alkenes

The first rhodium alkylidene square-planar complex stabilized by an N-heterocyclic carbene ligand, RhCl(-CHPh)(IPr)PPh3 (2; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-carbene), has been prepared by reaction of RhCl(IPr)(PPh3)2 (1) with phenyldiazomethane and its dynamic behavior in solution studied. Treatment of 2 with alkenes results in the formation of the ¿2-olefin complexes RhCl(¿2-CH2-CHR)(IPr)PPh3 (3, R = H; 4, R = Ph; 5, R = OEt) and new olefins arising from the coupling of the alkylidene with the alkenes, likely via a metallacyclobutane intermediate

Scaling the state: Egypt in the third millennium BC

Discussions of the early Egyptian state suffer from a weak consideration of scale. Egyptian archaeologists derive their arguments primarily from evidence of court cemeteries, elite tombs, and monuments of royal display. The material informs the analysis of kingship, early writing, and administration but it remains obscure how the core of the early Pharaonic state was embedded in the territory it claimed to administer. This paper suggests that the relationship between centre and hinterland is key for scaling the Egyptian state of the Old Kingdom (ca. 2,700-2,200 BC). Initially, central administration imagines Egypt using models at variance with provincial practice. The end of the Old Kingdom demarcates not the collapse, but the beginning of a large-scale state characterized by the coalescence of central and local models