Isotope ratio monitoring gas chromatography/Mass spectrometry of D/H by high temperature conversion isotope ratio mass spectrometry

Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd.     

Extended-ion approximation and pressure shifts inF-band energies

Pressure variation of maximumF-band absorption energies in the halides of lithium, sodium and potassium has been investigated employing the extended-ion approximation for the calculation of theF-electron energy eigenvalues and using values of local compressibility in the neighbourhood of theF-centres which include the effect of vacancy and pressure. The results obtained agree with the experimental results.     

Polarization dependent,surface plasmon induced photoconductance in gold nanorod arrays

We report on the photoconductance in two‐dimensional arrays of gold nanorods. The arrays are formed by a combination of droplet deposition and stamping methods. We find that the plasmon induced photoconductance is sensitive to the linear polarization of the exciting photons consistent with the excitation of the longitudinal surface plasmon resonance of the nanorods.

     

Resonant photoconductance of molecular junctions formed in gold nanoparticle arrays

We investigate the photoconductance properties of oligo(phenylene vinylene) (OPV) molecules in metal-molecule-metal junctions. The molecules are electrically contacted in a two-dimensional array of gold nanoparticles. The nanoparticles in such an array are separated by only few nanometers. This allows to bridge the distance between the nanoparticles with molecules considered as molecular wires such as OPV. We report on the photoconductance of electrically contacted OPV upon resonant optical excitation of the molecules. This resonant photoconductance is sublinear in laser intensity, which suggests that trap state dynamics of the optically excited charge carriers dominate the optoelectronic response.     

Diagrammatic structure of the general coupled cluster equations

The general formula for the number of diagrammatic terms occurring in the T_n equation within a particular coupled cluster model is derived. Both the antisymmetrized and Goldstone diagrams are considered. In addition to the full coupled cluster equation approximate approaches are discussed, and for each the general formula for the number of terms is given. Analogous expressions are presented for the number of diagrammatic terms contributing to the elements of the transformed Hamiltonian [Hbar] = e^?T He^T .