Methods for achieving ultra-low backgrounds in above-ground germanium detector systems

The authors have previously shown how to achieve a 40-fold reduction in system background for above-ground germanium detectors. Such systems are generally sufficient for examining small hydrogenous samples or samples of non-hydrogenous materials such as soil, glass, metals, etc. However, samples with a large hydrogen content yield a seriously degraded background due to a number of neutron-induced interactions, such as Compton scatter following hydrogen capture of thermalized neutrons. A study was performed to better understand the sources of thermal neutron flux in above-ground detector systems. The effects of different quantities of hydrogen in the sample were also examined. Methods are presented for additional lowering of system background for both hydrogenous and non-hydrogenous samples.     

Effects of ring strain on gas-phase rate constants. 3. NO3 radical reactions with cycloalkenes

Rate constants for the gas-phase reactions of NO₃ radicals with a series of cycloalkenes have been determined at 298 ± 2 K, using a relative rate technique. Using an equilibrium constant for the NO₂ + NO₃ ? N₂O₅ reactions of 3.4 × 10^?11 cm³ molecule^?1, the following rate constants (in units of 10^?13 cm³ molecule^?1 s^?1) were obtained: cyclopentene, 4.52 ± 0.52; cycloheptene, 4.71 ± 0.56; bicyclo[2.2.1]-2-heptene, 2.41 ± 0.28; bicyclo[2.2.2]-2-octene, 1.41 ± 0.17; bicyclo[2.2.1]-2,5-heptadiene, 9.92 ± 1.13; and 1,3,5-cycloheptatriene, 12.6 ± 2.9. When combined with previous literature rate constants for cyclohexene and 1,4-cyclohexadiene, these data show that the rate constants for the nonconjugated cycloalkenes studied depend to a first approximation on the number of double bonds and the degree and configuration of substitution per double bond. No obvious effects of ring strain energy on these NO₃ radical addition rate constants were observed. Our previous a priori predictive techniques for the alkenes and cycloalkenes can now be extended to strained cycloalkenes.     

Kinetics of the gas-phase reactions of the OH radical with (C2H5)3PO and (CH3O)2P(S)Cl at 296 ± 2 K

The kinetics of the gas-phase reactions of the OH radical with (C₂H₅O)₃PO and (CH₃O)₂P(S)Cl and of the reactions of NO₃ radicals and O₃ with (CH₃O)₂P(S)Cl have been studied at room temperature. Using a relative rate technique, the rate constants determined for the reactions of the OH radical with (C₂H₅O)₃PO and (CH₃O)₂P(S)Cl at 296 ± 2 K and 740 torr total pressure of air were (5.53 ± 0.35) × 10^?11 and (5.96 ± 0.38) × 10^?11 cm³ molecule^?1 s^?1, respectively. Upper limits to the rate constants for the NO₃ radical and O₃ reactions with (CH₃O)₂P(S)Cl of <3 × 10^?14 cm³ molecule^?1 s^?1 and <2 × 10^?19 cm³ molecule^?1 s^?1, respectively, were obtained. These data are compared and discussed with previous literature data for organophosphorus compounds.     

Crystal Structure and ESR Study of a Bimetallic Copper/Iron Crown Ether Inclusion Complex

Bimetallic inclusion complexes have been synthesized by a secondary coordination interaction between the guest complex [Fe(η⁵-C₅H₅)(CO)₂(NH₃)][PF₆] and copper(II) complex 1a or nickel(II) complex lb containing crown-ether hosts. The X-ray crystal-structure analysis established that the Cu,Fe inclusion complex 2 crystallize as a centrosymmetric dimer with a Cu? Cu separation of 3.73 Å and a novel out-of-plane Cu? N interaction. The magnetic parameters for 2 were obtained by ESR and ENDOR spectroscopy. ESR susceptibility measurements down to 6 K exclude the presence of any antiferromagnetic coupling interaction between the Cu^IIcenters of the dimer.     

Regioselectivity of nucleophilic additions to tricarbonyl[η5-2-methyl-2,4-cyclohexadien-1-yl]iron(1+)PF6-: temperature dependence of hydride reductions

Reduction of [(η⁵-CH₃C₆H₆)Fe(CO)₃]⁺PF₆^? by NaBH₄, LiBH₄, LiEt₃BH and KBu⁵₃BH becomes less regioselective at lower temperatures. Regioselectivity of reduction by 9-BBN, however, improves as the temperature is lowered. Factors affecting nucleophilic addition are discussed in terms of likely transition states for the competing processes.     

Formulation of a Ritz-Galerkin type procedure for the approximate solution of the neutron transport equation

The one-group neutron transport equation is commonly given as an integrodifferential equation for the neutron density ψ(x, ω) over a domain G × S in the five-dimensional phase space $\text{E}{}_3\text{× S(¦ ω ¦ = 1)}$. In this paper we show how, by decomposing the domain of the transport operator into a complementary pair of manifolds by means of a projection operator, any transport problem can be formulated, on either manifold, in terms of a symmetric positive definite operator. We use Friedrichs' method to extend the operator to a selfadjoint operator and look for a generalized solution by minimizing a certain functional over the appropriate Hilbert space. A Ritz-Galerkin type approximation procedure is formulated, and an estimate for the difference between the exact and approximate solution is given. The procedure is illustrated for a special choice of finite dimensional subspace.     

Reversible intermolecular energy transfer between saturated amines and benzene in non-polar solution

Excitation of a mixture of dimethylethylamine (DEMA) and benzene in n-hexane at 222 nm primarily produces excited amine, while at 261 nm excited benzene predominantly results. The fluorescence spectra appreciably overlap. With 222 nm excitation, DEMA fluorescence is quenched by benzene at the diffusion-controlled rate; this quenching results with nearly unit efficiency in sensitized benzene fluorescence. With 261 nm excitation, some sensitized DEMA fluorescence is observed: the rate constant for tins process is ≈ 2.6 × 10⁹ M^?1 s^?1.     

Streaming at the negative polarographic maximum of the first kind

A theory developed in a previous paper of the streaming of the electrolyte solution at the polarographic maximum of the first kind with the dropping mercury electrode, is applied to the negative maximum. Stream function contours and fluid velocities are calculated and comparison is made with the experimental results of O'Brien and Dieken. Calculated separations in flow below the neck of the mercury drop are in agreement with predictions of other authors.