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

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

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

Impact of mechanical deformation on space charge in XLPE

In this paper we report the effect of mechanical deformation on space charge dynamics in crosslinked polyethylene. Thin films were peeled from a 66 kV commercial XLPE cable. Space charge measurements under dc electric fields have been monitored using the pulsed electroacoustic (PEA) technique. It has been found that charge dynamics in deformed XLPE are different from that from undeformed XLPE at lower voltages. At low applied electric field, space charge is dominated by heterocharge in the deformed XLPE while homocharge governs charge formation in undeformed XLPE. However, at high electric field, there is no significant difference between them. Space charge is dominated by homocharge in both deformed and undeformed XLPE. The results indicated that through deformation, molecular chains rearrange so small molecules such as crosslinking by-products, initially being trapped, can be released. Under the influence of the applied electric field they can be ionised to form heterocharge in the sample

On fast radial propagation of parametrically excited geodesic acoustic mode

The spatial and temporal evolution of parametrically excited geodesic acoustic mode (GAM) initial pulse is investigated both analytically and numerically. Our results show that the nonlinearly excited GAM propagates at a group velocity which is, typically, much larger than that due to finite ion Larmor radius as predicted by the linear theory. The nonlinear dispersion relation of GAM driven by a finite amplitude drift wave pump is also derived, showing a nonlinear frequency increment of GAM. Further implications of these findings for interpreting experimental observations are also discussed