The HITRAN 2008 molecular spectroscopic database

This paper describes the status of the 2008 edition of the HITRAN molecular spectroscopic database. The new edition is the first official public release since the 2004 edition, although a number of crucial updates had been made available online since 2004. The HITRAN compilation consists of several components that serve as input for radiative-transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e. spectra in which the individual lines are not resolved; individual line parameters and absorption cross-sections for bands in the ultraviolet; refractive indices of aerosols, tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 42 molecules including many of their isotopologues.     

Dynamics of nitric oxide rebinding and escape in horseradish peroxidase

Ultrafast kinetic measurements of NO rebinding to horseradish peroxidase (HRP) are reported for the first time. The geminate kinetics are found to be exponential for all HRP samples studied. The ferric forms of HRP have NO geminate recombination time constants in the range of 15-30 ps, while the ferrous form has a time constant of approximately 7 ps. The simple exponential NO geminate kinetics found for HRP demonstrate that heme relaxation is not the underlying source of the nonexponential NO rebinding in myoglobin (Mb). The NO ligand escape rates from HRP are also determined, and they are found to depend dramatically on the presence or absence of the competitive inhibitor benzohydroxamic acid (BHA). The kinetic results indicate that, in contrast to Mb, there is direct solvent access to the distal heme pocket of HRP.     

Analysis of Algebraic Closures of the Mean Scalar Dissipation Rate of the Progress Variable Applied to Stagnating Turbulent Flames

In the turbulent premixed reactive flows considered in this study, i.e. large Damköhler and Reynolds numbers, the flamelet regime of turbulent combustion applies and the scalar dissipation rate and mean reaction rate are inter related. In this situation various algebraic models for the mean chemical rate that are obtained from an equilibrium of the dominant terms of the transport equation for the scalar dissipation rate, are evaluated through their application to flames stabilized in a turbulent stagnating flow. An asymptotic analysis is first performed and results obtained through the resulting one-dimensional calculation are compared with the experimental data of Li et al. (Proc Combust Inst 25:1207–1214, 1994). Eventually, three-dimensional CFD calculations including suited algebraic closures to represent the turbulent transport terms are carried out. Results are satisfactorily compared to the experimental data of Cho et al. (Proc Combust Inst 22:739–745, 1988). As a first outcome, the analysis confirms the interest and the relevance of the corresponding algebraic closures to deal with turbulent premixed combustion in such conditions. In the search of a satisfactory representation of such premixed impinging flames, the computational results also clearly emphasize the strong intertwinment that exits between the mean reaction rate, i.e. scalar dissipation rate or micro-mixing taking place at the smallest scale of the reactive flowfield, and the Reynolds fluxes modelling, i.e. turbulent macro-mixing.     

Study of α- and β-relaxation processes in supercooled sucrose liquids

The relaxation map of highly concentrated sucrose water mixtures was built using mechanical and impedance spectroscopies. Data of - and -relaxation processes obtained with both techniques complete calorimetric and rheological measurements. The temperature evolutions of the relaxations were extrapolated using the measured data and the equations commonly used to describe the relaxations: Arrhenius and WLF behaviours for respectively the - and -relaxations. The temperature/frequency domain when and processes merge for 99% sucrose solution is discussed with respect to scenery proposed in the literature.This revised version was published online in November 2005 with corrections to the Cover Date.     

Vortex flux channeling in magnetic nanoparticle chains

A detailed understanding of the formation of magnetic vortices in closely spaced ferromagnetic nanoparticles is important for the design of ultra-high-density magnetic devices. Here, we use electron holography and micromagnetic simulations to characterize three-dimensional magnetic vortices in chains of FeNi nanoparticles. We show that the diameters of the vortex cores depend sensitively on their orientation with respect to the chain axis and that vortex formation can be controlled by the presence of smaller particles in the chains.     

Vibration-rotation energies of harmonic and combination levels in tetrahedral XY4 molecules: Theory and extrapolation method

This paper presents a general method for studying overtones and combination bands of tetrahedral XY₄ molecules. Making full use of group theory, the matrix representation of the Hamiltonian restricted to any set of vibrational sublevels is easily derived from a basis of rovibrational matrices. Explicit expressions for the reduced matrix elements are developed for all the operators of any order occurring in states for which Σ_sv_s ≤ 2, including any interaction type. The parameters introduced are directly the Hamiltonian expansion coefficients and consequently have the same physical significance in any vibrational state. The treatment of overtones and combination bands for which the corresponding fundamentals are analyzed is considered in detail. In this case, the parameters of the ground and fundamental states remain fixed and only a few new parameters occurring specifically in the studied state need to be determined. In this way, the convergence of least-squares fits is greatly improved. The example of methane is used to illustrate the efficiency of this method suitable for the direct determination of potential constants.     

Analysis of the ν2 + ν3 band of 12CH4 and 13CH4

The ν₂ + ν₃ bands of ¹²CH₄ and ¹³CH₄ occurring in the region 4400–4650 cm^?1 have been studied from spectra recorded with a high-resolution Fourier transform spectrometer (resolution better than 0.01 cm^?1). Champion's Hamiltonian expansion, Canad. J. Phys.55, 1802 (1977), is applied to the problem of the two interacting F₁ and F₂ vibrational sublevels of this type of a band. As the P branch of ν₂ + ν₃ is strongly overlapped by neighboring bands, a combination-difference method, adapted to tetrahedral XY₄ molecules has been developed to help assignments of lines. A fit of 700 transitions has been performed using 13 new effective constants in the case of ¹²CH₄. In the case of ¹³CH₄, 532 transitions have been fit to 18 constants. The known parameters, relative to the vibrational ground state and the ν₃ state for both methanes, and the ν₂ state for ¹²CH₄ were fixed throughout. Most of the perturbed levels, up to J′ = 12, are well reproduced and the general agreement between experimental and calculated transitions is satisfactory with standard deviations of 0.047 cm^?1 (¹²CH₄) and 0.041 cm^?1 (¹³CH₄). The results (order of magnitude of obtained (ν₂ + ν₃) parameters and comparison of observed and computed intensities) indicate that the ν₂ + ν₃ band is perturbed by many other bands.     

Ion-induced secondary electron and negative ion emission from Mo/O

Absolute yields of secondary electrons and negative ions resulting from collisions of Na⁺ with Mo(100) and a polycrystalline molybdenum surface have been measured as a function of the oxygen coverage of the surface for impact energies below 500 eV. The sputtered negative ions have been identified with mass spectroscopy, and O⁻ is found to be the dominant sputtered negative ion for the surfaces at all oxygen coverages and impact energies. Both the electron and O⁻ yields have an impact energy threshold at about 50 eV and exhibit a strong dependence on oxygen coverage. The kinetic energy distributions of the secondary electrons and sputtered O⁻ were determined as functions of the oxygen coverage and impact energy. The distributions for O⁻ are characterized by a narrow low-energy peak (at 1–2 eV) followed by a low-level high-energy tail. The secondary electrons have a narrow (FWHM 1–2 eV) kinetic energy distribution, centered approximately at 1–2 eV. The shapes of the distributions and their most probable energies are essentially invariant with impact energy, oxygen coverage and the nature of the Mo surface. The emission is explained and analyzed in terms of a simple model which involves a collision-induced electronic excitation of the MoO⁻ surface state. The decay of this excited state leads to the production of both secondary electrons and O⁻ with energy distributions and yields comparable to those observed.