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At least 253 records · Page 14

Direct observation of coherence transfer and rotational-to-vibrational energy exchange in optically centrifuged CO2 super-rotors

Abstract Optical centrifuges are laser-based molecular traps that can rotationally accelerate molecules to energies rivalling or exceeding molecular bond energies. Here we report time and frequency-resolved ultrafast coherent Raman measurements of optically centrifuged CO 2 at 380 Torr spun to energies beyond its bond dissociation energy of 5.5 eV ( J max = 364, E rot = 6.14 eV, E rot / k B = 71, 200 K). The entire rotational ladder from J = 24 to J = 364 was resolved simultaneously which enabled a more accurate measurement of the centrifugal distortion constants for CO 2 . Remarkably, coherence transfer was directly observed, and time-resolved, during the field-free relaxation of the trap as rotational energy flowed into bending-mode vibrational excitation. Vibrationally excited CO 2 ( ν 2 > 3) was observed in the time-resolved spectra to populate after 3 mean collision times as a result of rotational-to-vibrational (R-V) energy transfer. Trajectory simulations show an optimal range of J for R-V energy transfer. Dephasing rates for molecules rotating up to 5.5 times during one collision were quantified. Very slow decays of the vibrational hot band rotational coherences suggest that they are sustained by coherence transfer and line mixing.

74 ATOMIC AND MOLECULAR PHYSICS↗

Relative intensity calculations for nitrous oxide.

A tabulation of calculated rotational line intensities, relative to the integrated intensity of a vibration-rotation band, is given for Sigma-Sigma, Pi-Sigma, Sigma-Pi, Pi-Pi, and Delta-Pi transitions of nitrous oxide. These calculations were made for temperatures of 250 K and 300 K. A summary of band-intensity measurements is also presented.

Young, L. D. G.↗

Feasibility study of the application of existing techniques to remotely monitor hydrochloric acid in the atmosphere

A critical evaluation of existing optical remote sensors for HCl vapor detection in solid propellant rocket plumes is presented. The P branch of the fundamental vibration-rotation band was selected as the most promising spectral feature to sense. A computation of transmittance for HCl vapor, an estimation of interferent spectra, the application of these spectra to computer modelled remote sensors, and a trade-off study for instrument recommendation are also included.

Zwick, H.↗

Properties of water vapor relevant to its measurement in the stratosphere and mesosphere

The literature on the concentrations of water vapor in the stratosphere and mesosphere was studied. It is estimated that the concentrations in these lie in the range from 0.1 ppm to 10 ppm. A survey was made of the scattering and radiative transfer properties of water vapor and the background constituents to determine the physical properties of importance to measurements of concentrations. It was determined that absorption and emission properties provide significant increases in sensitivity compared with the various scattering phenomena considered. Microwave absorption in the region of 22 GHz and 183 GHz and infrared absorption in the vibrational rotational band systems seem to be the most attractive techniques. Various experimental configurations are analyzed and compared.

Longbothum, R. L.↗

Time variation of the H2O maser and infrared continuum in late-type stars

Observations of the variability of the 1.35-cm H2O and 2.2-micron emission from eight late M stars are described. A comparison of the microwave and infrared variations is of interest because the bulk of the stellar energy is radiated in the near-infrared and because at least one theory (Litvak 1969) hypothesizes near-infrared maser pumping via the 2.7-micron H2O vibration-rotation band. Variations at the two wavelengths appear to be correlated and possible explanations for this correlation are discussed.

Schwartz, P. R.↗

Detection of O-17 in IRC+10216

Lines of the fundamental vibration-rotation band of C-12 O-17 have been observed near 4.7 micron in IRC+10216. Lines of C-12 O-18 were not detected, indicating a lower limit of 5 for the abundance ratio O-17/O-18. A lower limit of 200 and a probable value of 400 is obtained for the ratio O-16/O-17. The presence of C-12 O-17 is also indicated in alpha Her and alpha Sco.

Rank, D. M.↗

Investigation of nitric oxide decomposition in the temperature range 2500-4100 K

The decomposition of nitric oxide has been studied in the temperature range 2500-4100 K using a shock-tube technique. The principle result of the study was the determination of the rate constant (k) for the reaction O + NO yields N + O2. Mixtures of NO and N2O diluted in argon or krypton were heated by incident shock waves and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The experimental values of k are fit closely by the expression k = (2.36 times 10 to the 9th power) x T x exp(-38,640/RT) cm cu/mole-sec, which also provides a good fit to previous data at higher and lower temperatures.

Flower, W. L.↗

Thermodynamic derivatives of infrared absorptance

Calculation of the concentration, pressure, and temperature dependence of the spectral absorptance of a vibrational absorption band. A smooth thermodynamic dependence was found for wavelength intervals where the average absorptance is less than 0.65. Individual rotational lines, whose parameters are often well known, were used as bases in the calculation of medium resolution spectra. Two modes of calculation were combined: well-separated rotational lines plus interaction terms, or strongly overlapping lines that were represented by a compound line of similar shape plus corrections. The 1.9- and 6.3-micron bands of H2O and the 4.3-micron band of CO2 were examined in detail and compared with experiment.

Broersma, S.↗

Kinetics of the reaction of nitric oxide with hydrogen

Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The reaction kinetics were studied in the temperature range 2400-4500 K using a shock-tube technique. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principle result of the study was the determination of the rate constant for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k sub 1 were obtained for each test through comparisons of measured and numerically predicted NO profiles.

Flower, W. L.↗

The silicon monoxide radical and the atmosphere of alpha Orionis

We present new molecular constants, line positions, and transition probabilities for the first-overtone vibration-rotation bands in the X 1 Sigma+ electronic ground state of SiO, together with an estimate of the SiO abundance and silicon isotope ratios in the atmosphere of alpha Ori.

Beer, R.↗

U.S. National Congress of Applied Mechanics, 7th, University of Colorado, Boulder, Colo., June 3-7, 1974, Proceedings

A series of experimental, theoretical, and review papers dealing with various aspects of applied mechanics, including structural analysis, mathematical methods, and fluid dynamics. Some of the topics covered are: the direct formulation of two-dimensional mechanics problems, the mechanical aspects of athletics, Laplace's tidal equations, cochlear mechanics, dynamic constitutive equations, optical techniques for the determination of displacement and strain fields, chemical and biochemical problems involving nonlinear diffusion processes, thermal stresses, the rotating rod viscometer, finite-element methods in plasticity, ships of minimum resistance, and wide-band random vibration of structures. Individual items are announced in this issue.

Source record↗

Determination of the rate constant for the reaction O + NO yields N + O2

A shock-tube technique was used to determine the rate constant for the reaction O + NO yields N + O2 in the 2500-4100 K range. Mixtures of NO, N2O, and an inert gas (Ar or Kr) were shock-heated, and the decay of infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was monitored. The N2O dissociates quickly to provide a source of O atoms for the above reaction. An expression for the rate constant is derived which fits these data and previous data at higher and lower temperatures.

Hanson, R. K.↗

Kinetics of the reaction of nitric oxide with hydrogen

The reaction of nitric oxide with hydrogen has been studied in the temperature range 2400-4500 K using a shock-tube technique. Mixtures of NO and H2 diluted in argon or krypton were heated by incident shock waves, and the infrared emission from the fundamental vibration-rotation band of NO at 5.3 microns was used to monitor the time-varying NO concentration. The decomposition of nitric oxide behind the shock was found to be modeled well by a fifteen-reaction system. A principal result of the study was the determination of the rate constant k1 for the reaction H + NO yields N + OH, which may be the rate-limiting step for NO removal in some combustion systems. Experimental values of k1 were obtained for each test through comparisons of measured and numerically predicted NO profiles. The data are fit closely by the expression k1 = 1.34 times 10 to the fourteenth power exp(-49 200/RT) cu cm/mole-sec. These data appear to be the first available for this rate constant.

Flower, W. L.↗