Unimolecular Rovibrational Bound and Resonance States for Large Angular Momentum: J=20 Calculations for HO2

We explore the calculation of unimolecular bound states and resonances for deep-well species at large angular momentum using a Chebychev filter diagonalization scheme incorporating doubling of the autocorrelation function as presented recently by Neumaier and Mandelshtam [Phys. Rev. Lett. 86, 5031 (2001)]. The method has been employed to compute the challenging J=20 bound and resonance states for the HO2 system. The methodology has firstly been tested for J=2 in comparison with previous calculations, and then extended to J=20 using a parallel computing strategy. The quantum J-specific unimolecular dissociation rates for HO2-> H+O-2 in the energy range from 2.114 to 2.596 eV have been reported for the first time, and comparisons with the results of Troe and co-workers [J. Chem. Phys. 113, 11019 (2000) Phys. Chem. Chem. Phys. 2, 631 (2000)] from statistical adiabatic channel method/classical trajectory calculations have been made. For most of the energies, the reported statistical adiabatic channel method/classical trajectory rate constants agree well with the average of the fluctuating quantum-mechanical rates. Near the dissociation threshold, quantum rates fluctuate more severely, but their average is still in agreement with the statistical adiabatic channel method/classical trajectory results.

Sheet flow sediment transport under waves with acceleration skewness and boundary layer streaming

The effect of acceleration skewness on sheet flow sediment transport rates (q) over bar (s) is analysed using new data which have acceleration skewness and superimposed currents but no boundary layer streaming. Sediment mobilizing forces due to drag and to acceleration (similar to pressure gradients) are weighted by cosine and sine, respectively, of the angle phi(.)(tau)phi(tau) = 0 thus corresponds to drag dominated sediment transport, (q) over bar (s)similar to vertical bar u(infinity)vertical bar u(infinity), while phi(tau) = 90 degrees corresponds to total domination by the pressure gradients, (q) over bar similar to du(infinity)/dt. Using the optimal angle, phi = 51 degrees based on that data, good agreement is subsequently found with data that have strong influence from boundary layer streaming. Good agreement is also maintained with the large body of U-tube data simulating sine waves with superimposed currents and second-order Stokes waves, all of which have zero acceleration skewness. The recommended model can be applied to irregular waves with arbitrary shape as long as the assumption negligible time lag between forcing and sediment transport rate is valid. With respect to irregular waves, the model is much easier to apply than the competing wave-by-wave models. Issues for further model developments are identified through a comprehensive data review.