Fast iterative methods for symmetric sinc-Galerkin systems

The symmetric sinc-Galerkin method developed by Lund, when appliedto the second-order self-adjoint boundary value problem, givesrise to a symmetric coefficient matrix has a special structureso that it can be advantageously used in solving the discretesystem. In this paper, we employ the preconditioned conjugategradient method with banded matrices as preconditioners. Weprove that the condition number of the preconditioned matrixis uniformly bounded by a constant independent of the size ofthe matrix. In particular, we show that the solution of an n-by-ndiscrete symmetric sinc-Galerkin system can be obtained in O(nlog n) operations. We also extend our method to the self-adjointelliptic partial differential equation. Numerical results aregiven to illustrate the effectiveness of our fast iterativesolvers.     

Calculation of energies of excited states using MNDO

The energies of the lowest singlet (S₁) and triplet (T₁) states of 28 molecules have been calculated by the “half-electron” (MNDO -HE ) and spin-unrestricted (UMNDO ) versions of MNDO . While most of the calculated values are too negative, because of overestimation of the correlation energy in MNDO -HE and UMNDO , the errors are systematic and depend in an understandable way on the nature of the molecular orbitals (MO S) involved. When appropriate corrections are applied, the calculated energies agree with experiment almost as well as they do for ground states. This justifies the use of MNDO -HE or UMNDO for studies of excited state processes.     

Distribution analysis of membrane penetration of proteins by depth-dependent fluorescence quenching

A new approach is presented to evaluate the depth-dependent quenching of the fluorescence of membrane-bound probes and integral proteins. By utilizing at least three quenchers of known and distinctly different depths, the following parameters can be recovered: most probable depth of the probe; dispersion of the depth distribution, which will depend on the size of probe and fluctuations in its position; and quenching efficiency, which is related to the exposure of a particular fluorophore to the lipid phase. The exposure of tryptophan residues in integral proteins can be quantitatively determined with respect to the model compound (tryptophan octyl ester). The proposed method was applied to the investigation of membrane complexes of the bee venom melittin and cytochrome b₅.     

(e, 3e) Differential cross section of He (21 S) and He (23 S)

The angular distribution of the five-fold differential cross section for the electron impact double ionization of He (2¹ S) and He (2³ S) has been studied. The kinematical conditions for maxima/minima in the angular distribution for the two cases have been compared. The two-step process for the double ionization is found to contribute very little in the triplet case.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

Protons colliding with crystalline ice: proton reflection and collision induced water desorption at low incidence energies

We present results of classical trajectory (CT) calculations on the sticking of protons to the basal plane (0001) face of crystalline ice, for normal incidence at a surface temperature (Ts) of 80 K. The calculations were performed for moderately low incidence energies (Ei) ranging from 0.05 to 4.0 eV. Surprisingly, significant reflection is predicted at low values of Ei (< or = 0.2 eV) due to repulsive electrostatic interactions between the incident proton and the surface water molecules with one of their H-atoms pointing upward toward the gas phase. The sticking probability increases with Ei and converges to unity for Ei > or = 0.8 eV. In the case of sticking, the proton is trapped in the ice forming a Zundel complex (H5O2+), with an average binding energy of 9.9 eV with a standard deviation of 0.5 eV, independent of the value of Ei. In nearly all sticking trajectories, the proton is implanted into the ice surface, with a penetration depth that increases with Ei. The strong interaction with the neighboring water molecules leads to a local rupture of the hydrogen bonding network, resulting in collision induced desorption of water (puffing), a process that occurs with significant probability even at the lowest Ei considered. The probability of water desorption increases with Ei. In nearly all trajectories in which water desorption occurs, a single three-coordinated water molecule is desorbed from the topmost monolayer.     

Quantitative auger electron analysis of homogeneous binary alloys: Chromium in gold

Quantitative Auger electron analysis of Cr/Au alloys with up to 20% Cr has been accomplished. The surface composition of scribed areas were compared to bulk compositions and it was shown that corrections for variation of density, escape depth, and electron backscattering must be included; these corrections change the measured surface Cr concentrations by approximately 15%. Alloy sputter yield ratios have been calculated from surface concentrations after sputtering with Ar or Ne (0.5, 1.0, 1.5, and 2.0 keV). The sputter yield ratio of Cr to Au was 0.5 at 1% Cr (significant preferred sputtering) but was near unity at 20% Cr (no preferred sputtering). The sputter yield ratio was nearly independent of ion species and ion energy. The 2 keV argon ion sputter yields for pure Cr and Au were determined to be 2.0 and 7.9 atoms/ion, respectively. However, the 2 keV argon ion sputter yield for Au in the alloys drops rapidly from 7.9 atoms/ion for pure Au, to 5 atoms/ion at 10–20% Cr. The sputter yield for Cr in alloys (5 atoms/ion) is relatively independent of composition and is 2.5 times higher than the yield of pure Cr. No simple model is known by which pure elements sputter yields could be used to predict alloy sputtering behavior.     

Natural abundance nitrogen-15 n.m.r. spectroscopy. Spin–lattice relaxation in organic compounds

The small negative magnetogyric ratio (γ) of the ¹⁵N nucleus decreases the efficiency of ¹⁵N? ¹H dipole-dipole relaxation to about 25% of that for an analogous ¹³C nucleus. This may lead to greater competition from other relaxation mechanisms in ¹⁵N n.m.r. and consequent partial or total quenching of the negative nuclear Overhauser effect (NOE). In unfavorable circumstances nulling of the ¹⁵N resonance can occur. Previous ¹⁵N relaxation studies have examined isotopically enriched, low molecular weight compounds. The present study examines several small to intermediate size organic compounds containing nitrogen at natural isotopic abundance. In contrast to some of the earlier studies, ¹⁵N? ¹H dipolar relaxation was found to be dominant for protonated nitrogen atoms, even for two tertiary nitrogens (the tertiary amine nitrogen in 1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a] quinolizine and the oxime nitrogen in 3-methyl-2-pentanone ketoxime). The magnitude of the NOE and the moderate value of T₁ indicate effective dipolar relaxation from neighboring but not directly bonded protons in these cases. Nitro groups were found, as expected, to have predominant contributions from non-dipolar mechanisms, and in one case (2-methyl-2-nitro-1, 3-propanediol) signal nulling (NOE of η = ?1) was observed. The effect of paramagnetic impurities was demonstrated for ethanolamine, which contains a basic nitrogen. In this case T₁^DD(¹⁵N? ¹H) = 4·3 s; added Ni(acac)₂ at 1 × 10^?4 Molar reduced the ¹⁵N T₁ to 0·065 s and consequently the NOE to η = 0.     

FT–NMR investigation of 13C?11B coupling. A reappraisal

An earlier short communication on this topic reports some incorrect ¹¹B? ¹³C coupling parameters. The correct data are given together with some ¹⁰B coupling and isomer shift data.