On the theory of the CO+OH reaction, including H and C kinetic isotope effects

The effect of pressure, temperature, H/D isotopes, and C isotopes on the kinetics of the OH+CO reaction are investigated using Rice-Ramsperger-Kassel-Marcus theory. Pressure effects are treated with a step-ladder plus steady-state model and tunneling effects are included. New features include a treatment of the C isotope effect and a proposed nonstatistical effect in the reaction. The latter was prompted by existing kinetic results and molecular-beam data of Simons and co-workers [J. Phys. Chem. A 102, 9559 (1998); J. Chem. Phys. 112, 4557 (2000); 113, 3173 (2000)] on incomplete intramolecular energy transfer to the highest vibrational frequency mode in HOCO*. In treating the many kinetic properties two small customary vertical adjustments of the barriers of the two transition states were made. The resulting calculations show reasonable agreement with the experimental data on (1) the pressure and temperature dependence of the H/D effect, (2) the pressure-dependent 12C/13C isotope effect, (3) the strong non-Arrhenius behavior observed at low temperatures, (4) the high-temperature data, and (5) the pressure dependence of rate constants in various bath gases. The kinetic carbon isotopic effect is usually less than 10 per mil. A striking consequence of the nonstatistical assumption is the removal of a major discrepancy in a plot of the kOH+CO/kOD+CO ratio versus pressure. A prediction is made for the temperature dependence of the OD+CO reaction in the low-pressure limit at low temperatures

On the theory of the reaction rate of vibrationally excited CO molecules with OH radicals

The dependence of the rate of the reaction CO+OH-->H+CO2 on the CO-vibrational excitation is treated here theoretically. Both the Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant kRRKM and a nonstatistical modification knon [W.-C. Chen and R. A. Marcus, J. Chem. Phys. 123, 094307 (2005).] are used in the analysis. The experimentally measured rate constant shows an apparent (large error bars) decrease with increasing CO-vibrational temperature Tv over the range of Tv's studied, 298–1800 K. Both kRRKM(Tv) and knon(Tv) show the same trend over the Tv-range studied, but the knon(Tv) vs Tv plot shows a larger effect. The various trends can be understood in simple terms. The calculated rate constant kv decreases with increasing CO vibrational quantum number v, on going from v=0 to v=1, by factors of 1.5 and 3 in the RRKM and nonstatistical calculations, respectively. It then increases when v is increased further. These results can be regarded as a prediction when v state-selected rate constants become available

A summary of rotorcraft handling qualities research at NASA Ames Research Center

The objectives of the rotorcraft handling qualities research program at Ames Research Center are twofold: (1) to develop basic handling qualities design criteria to permit cost effective design decisions to be made for helicopters, and (2) to obtain basic handling qualities data for certification of new rotorcraft configurations. The research on the helicopter handling qualities criteria has focused primarily on military nap-of-the-earth (NOE) terrain flying missions, which are flown in day visual meteorological conditions (VMC) and instrument meteorological conditions (IMC), or at night. The Army has recently placed a great deal of emphasis on terrain flying tactics in order to survive and effectively complete the missions in modern and future combat environments. Unfortunately, the existing Military Specification MIL-H 8501A which is a 1961 update of a 1951 document, does not address the handling qualities requirements for terrain flying. The research effort is therefore aimed at filling the void and is being conducted jointly with the Army Aeromechanics Laboratory at Ames. The research on rotorcraft airworthiness standards with respect to flying qualities requirements was conducted to collaboration with the Federal Aviation Administration (FAA)

Monomial Testing and Applications

In this paper, we devise two algorithms for the problem of testing $q$-monomials of degree $k$ in any multivariate polynomial represented by a circuit, regardless of the primality of $q$. One is an $O^*(2^k)$ time randomized algorithm. The other is an $O^*(12.8^k)$ time deterministic algorithm for the same $q$-monomial testing problem but requiring the polynomials to be represented by tree-like circuits. Several applications of $q$-monomial testing are also given, including a deterministic $O^*(12.8^{mk})$ upper bound for the $m$-set $k$-packing problem.Comment: 17 pages, 4 figures, submitted FAW-AAIM 2013. arXiv admin note: substantial text overlap with arXiv:1302.5898; and text overlap with arXiv:1007.2675, arXiv:1007.2678, arXiv:1007.2673 by other author

The finite-temperature thermodynamics of a trapped unitary Fermi gas within fractional exclusion statistics

We utilize a fractional exclusion statistics of Haldane and Wu hypothesis to study the thermodynamics of a unitary Fermi gas trapped in a harmonic oscillator potential at ultra-low finite temperature. The entropy per particle as a function of the energy per particle and energy per particle versus rescaled temperature are numerically compared with the experimental data. The study shows that, except the chemical potential behavior, there exists a reasonable consistency between the experimental measurement and theoretical attempt for the entropy and energy per particle. In the fractional exclusion statistics formalism, the behavior of the isochore heat capacity for a trapped unitary Fermi gas is also analyzed.Comment: 6 pages, 6 figure

Isotopomer Fractionation in the UV Photolysis of N_2O: 3. 3D Ab Initio Surfaces and Anharmonic Effects

The wavelength-dependent isotopic fractionation of N_2O is calculated, extending our previous work, Parts 1 and 2, in several aspects: (1) the fully three-dimensional ab initio electronic potential and transition dipole moment surfaces of S. Nanbu and M. S. Johnson (J. Chem. Phys. A 2004, 108, 8905) are used to calculate the absorption cross sections, instead of a 2D surface and (2) the vibrational frequencies and wave functions with anharmonicity correction are used for the ground electronic state. The results for the absorption spectrum and for the isotopic fractionation of the different isotopomers are discussed. One difference between experiments measuring the absorption coefficient (von Hessberg et al. Atmos. Chem. Phys. 2004, 4, 1237) and the others that measure instead the photodissociation is also discussed. Experiments on the quantum yield for wavelengths longer than 200 nm (>50000 cm^(−1)) would be helpful in treating the observed difference

A theoretical study of ozone isotopic effects using a modified ab initio potential energy surface

A modified ab initio potential energy surface (PES) is used for calculations of ozone recombination and isotopic exchange rate constants. The calculated low-pressure isotopic effects on the ozone formation reaction are consistent with the experimental results and with the theoretical results obtained earlier [J. Chem. Phys. 116, 137 (2002)]. They are thereby relatively insensitive to the properties of these PES. The topics discussed include the dependence of the calculated low-pressure recombination rate constant on the hindered-rotor PES, the role of the asymmetry of the potential for a general X + YZ reaction (Y[not-equal]Z), and the partitioning to form each of the two recombination products: XYZ and XZY

An Alternative to Spinning Dust for the Microwave Emission of LPH 201.663+1.643: an Ultracompact HII Region

The microwave spectral energy distribution of the dusty, diffuse H II region LPH 201.663+1.643 has been interpreted by others as tentative evidence for microwave emission from spinning dust grains. We present an alternative interpretation for that particular object; specifically, that an ultracompact H II region embedded within the dust cloud would explain the available observations as well or better than spinning dust. Parameters for the size, surface brightness, and flux density of the putative ultracompact HII region, derived from the microwave observations, are within known ranges. A possible candidate for such an ultracompact H II region is IRAS 06337+1051, based upon its infrared colors. However, IRAS 06337+1051's infrared flux appears to be too small to be consistent with the microwave flux required for this alternative model to explain the observations.Comment: 11 pages, 3 figures, accepted to ApJ Letter