The quantum efficiency of the primary processes in formaldehyde photolysis at 3130 Å and 25°C

The mechanism of the photolysis of formaldehyde was studied in experiments at 3130 Å and in the pressure range of 1–12 torr at 25°C. The experiments were designed to establish the quantum yields of the primary decomposition steps (1) and (2), CH₂O + hν → H + HCO (1): CH₂O + hν → H₂ + CO (2), through the effects of added isobutene, trimethylsilane, and nitric oxide on Φ_CO and Φ. The ratio Φ_CO/Φ was found to be 1.01 ± 0.09(2σ) and (Φ + Φ_CO)/2 = 1.10 ± 0.08 over the range of pressures and a 12-fold change in incident light intensity. Isobutene and nitric oxide additions reduced Φ to about the same limiting value, 0.32 ± 0.03 and 0.34 ± 0.04, respectively, but these added gases differed in their effects on Φ_CO. With isobutene addition Φ_CO/Φ reached a limiting value of 2.3; with NO addition Φ_CO exceeded unity. The addition of small amounts of Me₃SiH reduced Φ to 1.02 ± 0.08 and lowered Φ_CO to 0.7. These findings were rationalized in terms of a mechanism in which the “nonscavengeable,” molecular hydrogen is formed in reaction (2) with ?₂ = 0.32 ± 0.03, while the “free radical” hydrogen is formed in reaction (1) with ?₁ = 0.68 ± 0.03. In the pure formaldehyde system these reactions are followed by (3)–(5): H + CH₂O → H₂ + HCO (3); 2HCO → CH₂O + CO (4); 2HCO → H₂ + 2CO (5). The data suggest k₄/k₅ ? 5.8. Isobutene reduced Φ by the reaction H + iso-C₄H₈ → C₄H₉ (20), and the results give k₂₀/k₃ ? 43 ± 4, in good agreement with the ratio of the reported values of the individual constants k₃ and k₂₀.     

Die Säuredissoziationskonstanten von O,O-Dialkyl-Estern der Aroylamido-thiophosphorsäuren in Äthanol—Wasser-Mischungen

Zusammenfassung Die Säuredissoziationskonstanten von O,O-Dialkyl-ester der Aroylamido-thiophosphorsäuren wurden in Äthanol-Wasser-Mischungen potentiometrisch bestimmt. Die experimentellen Angaben bestätigen bei einigen Vertretern dieser Verbindungsgruppe die Gleichung I^*, bei anderen die Gleichung II^**. Die charakteristischen Konstanten dieser Gleichungen werden ermittelt.

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Ionization Constants of O,O-Dialkyl aroylamido-thiophosphonates in ethanol—Water mixtures

The dissociation constants of O,O-dialkyl esters of aroylamido-thiophosphoric acids have been determined potentiometrically in ethanol-water mixtures. Some compounds of this group obey equation I^*, others equation II^**. The constants of these equations have been determined.

     

Cl-atom transfer from CFCl3 to the c-C6H11 radical. An indirect estimation of the CFCl2?Cl bond dissociation energy

The Cl-transfer reaction between CFCl₃ and c-C₆H₁₁ radicals (R) was studied in liquid cyclohexane (RH). The Arrhenius parameters for Cl abstraction were determined in the RH-CFCl₃ system versus the termination reaction between cyclohexyl radicals and competitively versus addition to C₂Cl₄ in the RH-CFCl₃-C₂Cl₄ system. The two sets of results are in very good agreement and give the following Arrhenius expression for the reaction R + CFCL₃ → RCl + CFCl₂ (2): where θ = 2.303RT in kcal/mol. Comparison with Cl-transfer data of other chloromethanes and chloroethanes shows that an increase in the C? Cl bond dissociation energy is the main cause of the reduced reactivity of CFCl₃. Based on a previously developed correlation, D(CFCl₂ ? Cl) is estimated to be equal to 74.4 kcal/mol.     

Turing invariant sets and the perfect set property

We show that $\text{◂...▸}\mathsf{ZF}+\mathsf{DC}+\text{“all}\text{Turing}\text{invariant}\text{sets}\text{of}\text{reals}\text{have}\text{the}\text{perfect}\text{set}\text{property”}$ implies that all sets of reals have the perfect set property. We also show that this result generalizes to all countable analytic equivalence relations.     

Thermally and optically stimulated luminescence in LiF:Mg,Ti: Application to mixed high/low ionization density radiation dosimetry

The viability of the concepts of using existing molecular nanostructures in LiF:Mg,Ti as solid-state nanodosimeters has been demonstrated. The concepts are based on mimicking radiobiology (specifically the ionization density dependence of double strand breaks in DNA) by using the similar ionization density dependence of electron-hole capture in spatially correlated TC/LC in the thermoluminescence and the identification of OSL with the “two-hit” F₂ center.     

Subthreshold regime in rubrene single-crystal organic transistors

Organic field-effect transistors were fabricated with vapor-grown rubrene single crystals in a staggered top-contact configuration. The devices were electrically characterized by measuring the transfer curves at low drain voltage. In parallel to these measurements, a model is developed to account for the subthreshold regime of the transistors. The model is based on the multiple trapping and thermal release concept, which assumes that charge transport is limited by a single level of shallow traps located close to the transport band edge. It is shown that the threshold voltage no longer establishes at the transition between the depletion and accumulation regimes. Instead, the threshold corresponds to the point at which traps are filled. This results in a subthreshold current that varies linearly with gate voltage. Moreover, the subthreshold current at low drain voltages increases with drain voltage. These finding are in good agreement with the experimental data.     

Neutron star structure and the neutron radius of 208Pb.

We study relationships between the neutron-rich skin of a heavy nucleus and the properties of neutron-star crusts. Relativistic effective field theories with a thicker neutron skin in 208Pb have a larger electron fraction and a lower liquid-to-solid transition density for neutron-rich matter. These properties are determined by the density dependence of the symmetry energy which we vary by adding nonlinear couplings between isoscalar and isovector mesons. An accurate measurement of the neutron radius in 208Pb-via parity violating electron scattering-may have important implications for the structure of the crust of neutron stars.     

Exact Formula for Currents in Strongly Pumped Diffusive Systems

We analyze a generic model of mesoscopic machines driven by the nonadiabatic variation of external parameters. We derive a formula for the probability current; as a consequence we obtain a no-pumping theorem for cyclic processes satisfying detailed balance and demonstrate that the rectification of current requires broken spatial symmetry.     

Mean field theory and the SU(2) adjoint Higgs model

Three versions of the mean field approximation are applied to determine the phase diagram of the SU(2) adjoint Higgs model. In two of these, one with gauge fixing and one without, the Higgs action is integrated exactly. In the third version, the Higgs and Wilson parts of the action are treated on equal footing. The results, when compared to those from Monte Carlo simulations, suggest that more accurate simulations are needed in the crossover region.     

The efficient frontier for spot and forward purchases: an application to electricity

A local electricity distribution company (LDC) can reduce its exposure to the inherent risks of spot-price volatility and uncertain future demand via forward contracts. Management's problem is to determine the optimal forward-contract purchase. We propose a practical three-stage approach for dealing with the problem. The first stage determines an optimal purchase by solving a cost-constrained risk-minimization problem. The second stage derives the efficient frontier of tradeoffs between expected cost and cost risk from the first-stage solution, at various bounds on the expected cost. The optimal solution is found by melding the frontier with management's risk preferences. In the third stage, the model's parameters are estimated from data typically available to an LDC and used to determine its forward-contract purchase.