SCF molecular orbital studies of internal rotation in the monofluorobenzaldehydes

The potential function for internal rotation of the aldehyde group in the orthometa- and para-fluorobenzaldehydes is calculated by CNDO/2, INDO and STO/6G methods, assuming invariant bond lengths. The INDO and STO/6G calculations indicate the equilibrium geometry to be essentially planar and the barrier to internal rotation to be the potential energy of the molecule when the plane of the aldehyde group is perpendicular to the ring plane; CNDO/2 leads to different conclusions, however. Relative stabilities of O-cis and O-trans rotamers of the planar configuration are discussed. Comparisons are made with the V barriers and the enthalpies of activation as determined by the dielectric absorption method using a matrix technique.     

The ring-opening of an unsymmetrical tetrahedral intermediate - 2-hydroxy-1,3-oxathiolane

Ab initio calculations were performed on 2-hydroxy-1,3-oxathiolane: and the two products of its breakdown: Complete geometry optimizations were performed at minimal (STO-3G) and split-valence (3-21G) basis set levels. In addition, a single point calculation was performed at 6-31G* level withd orbitals added on sulfur only. The conformation of the oxathiolane intermediate and its stability relative to the breakdown products was investigated. The STO-3G basis set gave an envelope form while 3-21G gave the twist form of the five-membered ring as the most stable. For all three basis sets the ester product was more stable than thioester.     

Lasers and optics: looking towards third generation gravitational wave detectors

Third generation terrestrial interferometric gravitational wave detectors will likely require significant advances in laser and optical technologies to reduce two of the main limiting noise sources: thermal noise due to mirror coatings and quantum noise arising from a combination of shot noise and radiation pressure noise. Increases in laser power and possible changes of the operational wavelength require new high power laser sources and new electro-optic modulators and Faraday isolators. Squeezed light can be used to further reduce the quantum noise while nano-structured optical components can be used to reduce or eliminate mirror coating thermal noise as well as to implement all-reflective interferometer configurations to avoid thermal effects in mirror substrates. This paper is intended to give an overview on the current state-of-the-art and future trends in these areas of ongoing research and development.     

Molecular orientation of asphaltenes and PAH model compounds in Langmuir-Blodgett films using sum frequency generation spectroscopy

Asphaltenes are an important class of compounds in crude oil whose surface activity is important for establishing reservoir rock wettability which impacts reservoir drainage. While many phenomenological interfacial studies with crude oils and asphaltenes have been reported, there is very little known about the molecular level interactions between asphaltenes and mineral surfaces. In this study, we analyze Langmuir-Blodgett films of asphaltenes and related model compounds with sum frequency generation (SFG) vibrational spectroscopy. In SFG, the polarization of the input (vis, IR) and output (SFG) beams can be varied, which allows the orientation of different functional groups at the interface to be determined. SFG clearly indicates that asphaltene polycyclic aromatic hydrocarbons (PAHs) are highly oriented in the plane of the interface and that the peripheral alkanes are transverse to the interface. In contrast, model compounds with oxygen functionality have PAHs oriented transverse to the interface. Computational quantum chemistry is used to support corresponding band assignments, enabling robust determination of functional group orientations.     

Direct sample fraction deposition using electrospray in narrow-bore size-exclusion chromatography/matrix-assisted laser desorption/ionization time-of-flight mass spectrometry for polymer characterization

A direct sample fraction deposition method was developed for off-line size-exclusion chromatography (SEC)/matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry. By using electrospray, the SEC eluent, together with a suitable matrix solution added coaxially, was directly deposited on the MALDI plate. Owing to the formation of very small droplets in electrospray, solvent evaporation is much faster. The fractionation volume in narrow-bore SEC, which can directly be collected in one MALDI spot, can easily be optimized in the range of a few microlitres. In addition, fairly homogeneous sample spots were obtained. The possible influence of composition variation of the SEC effluent on the analytical results using direct fraction deposition was investigated; no substantial effects were observed. The applicability of the method was demonstrated by characterizing a broad poly(methyl methacrylate) sample. Copyright 2000 John Wiley & Sons, Ltd.