C-Cl Bond Fission, Hcl Elimination, And Secondary Radical Decomposition In The 193 Nm Photodissociation Of Allyl Chloride

The primary photodissociation dynamics of allyl chloride upon excitation at 193 nm is investigated in a crossed laser-molecular beam scattering apparatus. Tunable vacuum ultraviolet (VUV) photoionization of the products provides a unique ability to learn about the secondary reaction products of the nascent photoproducts formed. The data show evidence for four significant primary reaction channels: a previously unidentified low kinetic energy C-Cl bond fission channel producing unstable allyl radicals, an excited state C-Cl bond fission channel producing Cl atoms with high translational energy, an HCl elimination pathway releasing significant energy to product translation to HCl and its momentum-matched mass 40 partner, and an HCl elimination channel producing low kinetic energy HCl products and predominantly unstable mass 40 products. The measured branching of these primary reaction channels of [all C-Cl] : [fast C-Cl] : [slow C-Cl] : [fast HCl] : [slow HCl] : [all HCl] is 1.00: 0.971: 0.029: 0.291: 0.167: 0.458 (where fast refers to the high recoil kinetic energy channels). The high internal energy allyl radicals formed in the slow C-Cl fission pathway of allyl chloride further dissociate/isomerize, as do the unstable mass 40 products formed in the HCl elimination pathways, and these products are investigated. Photoionization efficiency (PIE) curves of the HCl product suggest that a three-centered elimination mechanism contributes significantly to an observed HCl elimination reaction. (C) 2002 American Institute of Physics

Cluster evolution in steady-state two-phase flow in porous media

We report numerical studies of the cluster development of two-phase flow in a steady-state environment of porous media. This is done by including biperiodic boundary conditions in a two-dimensional flow simulator. Initial transients of wetting and non-wetting phases that evolve before steady-state has occurred, undergo a cross-over where every initial patterns are broken up. For flow dominated by capillary effects with capillary numbers in order of $10^{-5}$, we find that around a critical saturation of non-wetting fluid the non-wetting clusters of size $s$ have a power-law distribution $n_s \sim s^{-\tau}$ with the exponent $\tau = 1.92 \pm 0.04$ for large clusters. This is a lower value than the result for ordinary percolation. We also present scaling relation and time evolution of the structure and global pressure.Comment: 12 pages, 11 figures. Minor corrections. Accepted for publication in Phys. Rev.

Self-Affinity in the Gradient Percolation Problem

We study the scaling properties of the solid-on-solid front of the infinite cluster in two-dimensional gradient percolation. We show that such an object is self affine with a Hurst exponent equal to 2/3 up to a cutoff-length proportional to the gradient to the power (-4/7). Beyond this length scale, the front position has the character of uncorrelated noise. Importantly, the self-affine behavior is robust even after removing local jumps of the front. The previously observed multi affinity, is due to the dominance of overhangs at small distances in the structure function. This is a crossover effect.Comment: 4 pages, 4 figure

Developing Primary Propulsion for the Ares I Crew Launch Vehicle and Ares V Cargo Launch Vehicle

In accordance with the U.S. Vision for Space Exploration, NASA has been tasked to send human beings to the moon, Mars, and beyond. The first stage of NASA's new Ares I crew launch vehicle (Figure 1), which will loft the Orion crew exploration vehicle into low-Earth orbit early next decade, will consist of a Space Shuttle-derived five-segment Reusable Solid Rocket Booster (RSRB); a pair of similar RSRBs also will be used on the Ares V cargo launch vehicle's core stage propulsion system. This paper will discuss the basis for choosing this particular propulsion system; describe the activities the Exploration Launch Projects (ELP) Office is engaged in at present to develop the first stage; and offer a preview of future development activities related to the first Ares l integrated test flight, which is planned for 2009

Economic inequalities in the effectiveness of a primary care intervention for depression and suicidal ideation.

BACKGROUND: Economic disadvantage is associated with depression and suicide. We sought to determine whether economic disadvantage reduces the effectiveness of depression treatments received in primary care. METHODS: We conducted differential-effects analyses of the Prevention of Suicide in Primary Care Elderly: Collaborative Trial, a primary-care-based randomized, controlled trial for late-life depression and suicidal ideation conducted between 1999 and 2001, which included 514 patients with major depression or clinically significant minor depression. RESULTS: The intervention effect, defined as change in depressive symptoms from baseline, was stronger among persons reporting financial strain at baseline (differential effect size = -4.5 Hamilton Depression Rating Scale points across the study period [95% confidence interval = -8.6 to -0.3]). We found similar evidence for effect modification by neighborhood poverty, although the intervention effect weakened after the initial 4 months of the trial for participants residing in poor neighborhoods. There was no evidence of substantial differences in the effectiveness of the intervention on suicidal ideation and depression remission by economic disadvantage. CONCLUSIONS: Economic conditions moderated the effectiveness of primary-care-based treatment for late-life depression. Financially strained individuals benefited more from the intervention; we speculate this was because of the enhanced treatment management protocol, which led to a greater improvement in the care received by these persons. People living in poor neighborhoods experienced only temporary benefit from the intervention. Thus, multiple aspects of economic disadvantage affect depression treatment outcomes; additional work is needed to understand the underlying mechanisms