Accurate electrical and spectroscopic properties ofX 1Σ+ BeO from coupled-cluster methods

Summary This paper reports a series of coupled-cluster (CC) calculations through CCSDT on the theoretically challenging ground state of the BeO molecule. Along with CC methods, quadratic configuration interaction (QCI) approximations to CC theory have been used (QCISD and QCISD(T)), which show several dramatic failings. Equilibrium electrical properties (, _xx , and _zz ) and basic spectroscopic properties (r _e, _e,D _e, and infrared intensity (I)) have been computed. Basis set and electron correlation effects are analyzed in order to arrive at accurate values of the dipole moment and polarizability, which are not known experimentally. For the dipole moment, we obtain a value of 6.25 D, with an uncertainty of about 0.1 D. For _xx and _zz , we suggest respective values of 32 and 36 atomic units (a.u.) and error bars of about 1 and 2 a.u. With extended basis sets, the spectroscopic propertiesr _e, _e, andD _e are reproduced to high accuracy, which is the first time this has been achieved for this species byab initio methods. At the highest calculation levels,I is predicted to be very small. AlthoughI has not been measured, some support for this prediction comes from a recent infrared study of BeO-rare gas complexes. The QCI methods are shown to be much more sensitive to basis set, and even with large basis sets yield values of _zz andI which differ from CC results by an order of magnitude and three orders of magnitude, respectively. These differences doubtless arise from the importance of single excitations (T ₁) for this molecule, as several terms involvingT ₁ are neglected in the QCISD approximation compared with CCSD. We also report CC calculations with Brueckner orbitals, which yield results similar to those obtained with restricted Hartree-Fock orbitals.     

Growth and decay tables for radium-225 and actinium-225

To facilitate the use of²²⁵Ra as a yield tracer in radiochemical assays of²²⁶Ra and²²⁸Ra, growth and decay tables for²²⁵Ra, and its daughter²²⁵Ac, have been computed.     

Theoretical treatment of multiple site reactivity in large molecules

The method of electrostatic potentials is generalized via a double perturbation theory to describe the simultaneous attack of a large molecule by two or more charged species. The interaction term is found to reproduce accurately the full “super-molecule” calculation. The scheme is illustrated by treating the diprotonation of adenine and N7-methyladenine. For adenine, the most stable diprotonated species is found to be the N1, N7 combination, while the N3, N9 couple is predicted for the N7 substituted derivative if N3 is the first protonation site.     

Determination of the lipid peroxidation product trans-4-hydroxy-2-nonenal in biological samples by high-performance liquid chromatography and combined capillary column gas chromatography-negative-ion chemical ionisation mass spectrometry

trans-4-Hydroxy-2-nonenal (HNE) is an aldehyde end-product of lipid peroxidation in biological systems which is capable of producing a range of powerful biological effects. We wish to describe a sensitive and selective strategy for the determination of HNE in biological samples. The method is based on the formation of the O-pentafluorobenzyl (O-PFB) oxime derivatives of HNE and its deuterated internal standard which, after sample clean-up by solid-phase extraction and purification by high-performance liquid chromatography (HPLC), were derivatised further to trimethylsilyl ethers. Subsequent capillary column gas chromatography-negative-ion chemical ionisation mass spectrometry (GC-NICIMS) using selected-ion monitoring allowed quantitation in the low ng/ml range. The use of an internal standard and the O-PFB oxime derivatives circumvented the problems encountered previously by other workers because of the volatility and instability of HNE. The syn-isomer of HNE O-PFB oxime followed the anti-isomer on the HPLC and GC columns used, giving a distinctive pair of peaks of characteristic relative proportion. Moreover, the NICI mass spectra of the geometrical isomers were significantly different, providing further evidence to validate the identity of any endogenous HNE recovered. The method was used to identify and quantify HNE in platelets, monocytes, plasma and oxidised low-density lipoprotein.     

Electrophilic lactonization as a tool in acyclic stereocontrol. Synthesis of serricornin

Several electrophilic lactonization procedures have been explored as a means of functionalizing olefinic carboxylic acids with relative asymmetric induction, Iodolactonization of δ,? -unsaturated acids under conditions of thermodynamic control exhibits good 1,2- and 1,3-, but not 1,4-induction in the formation of δ-lactones. Mercurilactonization proceeds with good stereocontrol in the formation of both γ- and δ-lactones (1,2-induction), but suffers from the difficulty of elimination during reductive demercuration; phenylselenolactonization with N-(phenylseleno)phthalimide is apparently kinetically controlled, affording high induction with 10, a strongly sterically biased substrate leading to a δ-lactone, but not with 16, which leads to a γ-lactone. In contrast, hydroxymethyllactonization proceeds with good stereocontrol in the case of 26, the ester of 10, but not with the analogous ester of 16. The lactones resulting from cyclization of 10 and 13 were converted in stereospecific fashion into each of the stereoisomers of(±)-serricornin.     

Search for neutral, long-lived particles decaying into two muons in pp[over] collisions at sqrt[s]=1.96 TeV

We present a search for a neutral particle, pair produced in pp[over] collisions at sqrt[s]=1.96 TeV, which decays into two muons and lives long enough to travel at least 5 cm before decaying. The analysis uses approximately 380 pb(-1) of data recorded with the D0 detector. The background is estimated to be about one event. No candidates are observed, and limits are set on the pair-production cross section times branching fraction into dimuons + X for such particles. For a mass of 10 GeV and lifetime of 4x10(-11) s, we exclude values greater than 0.14 pb (95% C.L.). These results are used to limit the interpretation of NuTeV's excess of dimuon events.