Quasi-classical Trajectory Study of the Intramolecular Isotope Effect in the Reaction O（3p）＋H2/HD

Theoretical studies of the dynamics of the reactions O（3p）＋H2/HD（ν=0, j=0）→OH＋H have been performed with quasi-classical trajectory method （QCT） on an ab initio potential surface for the lowest triplet electronic state of H2O（aA＂）. The QCT-calculated integral cross sections are in good agreement with the earlier time-dependent quantum mechanics results. The state-resolved rotational distributions reveal that the product OH rotational distributions for O＋HD have a preference for populating highly internally excited states compared with the O＋H2 reaction. Distributions of differential cross sections show that directions of scattering are strongly dependent on the choice of quantum state. The polarization dependent generalized differential cross-sections and the distributions were calculated and a pronounced isotopic effect is revealed. The calculated results indicate that the product polarization is very sensitive to the mass factor.     

Isotope effects in the infrared spectra of the polar and nonpolar isomers of N2O dimer

The rotationally resolved spectra of ¹⁵N¹⁵N¹⁶O dimer for the polar and nonpolar isomers are studied in the region of the N-N stretching fundamental of the monomer (∼2150 cm⁻¹) using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. These spectra are very similar to the corresponding spectra of the normal species, (¹⁴N¹⁴N¹⁶O)₂. Structural parameters and vibrational shifts obtained here are compared with those of the normal species and ab initio values. These results confirm that the nonpolar isomer has a centrosymmetric slipped-antiparallel structure while the polar isomer consists of two slipped and (approximately) parallel monomer units.     

Vibronic intensity distribution in the B0u-X0g and B1u-X1g transition of Se2

The B0_u⁺-X0_g⁺ and B1_u-X1_g transitions of ⁸⁰Se₂ and ⁷⁸Se₂ are reinvestigated. Several new bands are reported, especially for the B1_u-X1_g system, their vibrational numbering being confirmed by isotope shift studies. The Franck-Condon factors and r-centroid values are evaluated. By correlating the theoretically computed intensities with observed values, the internuclear distance dependence of the electronic transition moments of these two systems is determined for the first time.     

The use of ICPMS for stable isotope tracer studies in humans: a review

The use of stable isotope tracers in human studies is a rapidly growing research field that benefits from the many new developments in inorganic mass spectrometric instrumentation and from the better availability of mass spectrometric techniques to nutritional scientists during the last three decades. Traditionally, thermal ionization mass spectrometry (TIMS) has been the preferred technique for these studies, but the development of new inductively coupled plasma mass spectrometric (ICPMS) techniques with better isotope-ratio measurement and interference-removal capabilities (e.g. single and multi-detector ICPMS and reaction/collision cell ICPMS) has enabled broader use of ICPMS for determination of stable isotope tracers in nutritional research. This review discusses the current and future use of ICPMS in stable isotope tracer studies in humans.     

Ultratrace analysis and isotope ratio measurements of long-lived radioisotopes by resonance ionization mass spectrometry (RIMS)

Resonance Ionization Mass Spectrometry (RIMS) is a sensitive and selective method for ultratrace analysis of long-lived radioisotopes and isotope ratio measurements. It provides extremely high isobaric suppression and good overall efficiency. The experimental limits of detection are as low as 10⁶ atoms per sample and isotopic selectivities of 5×10¹² have been obtained. The widespread potential of RIMS, using different experimental arrangements, is demonstrated for the determination of the radiotoxic isotopes Pu-238 to Pu-244 and Sr-89/Sr-90 in various environmental samples as well as for Ca-41 in nuclear reactor components and biomedical samples.     

Integrated target-ion source unit for on-line production of radioactive short-lived isotopes

A new version of integrated target-ion source unit (ionising target) has been developed for the on-line production of radioactive single-charged ions. The target is able to withstand temperatures up to 2500 ^°C and acts also as an ion source of the surface and laser ionisation. Off-line and on-line experiments with the ionising target, housing tantalum foils as a target material, have been carried out at the IRIS (Investigation of Radioactive Isotopes on Synchrocyclotron) facility. The off-line surface ionisation efficiency measured for stable atoms of Li, Rb and Cs was correspondingly 6% , 40% and 55% at the target temperature of 2000 ^°C and 3-10% for atoms of rare-earth elements Sm, Eu, Tm and Yb at a temperature of 2200 ^°C. The off-line measured values of the ionisation efficiency for stable Gd and Eu atoms by the laser beam ionisation inside the target were 1% and 7%, respectively. The radioactive beam intensities of neutron-deficient rare-earth nuclides from Eu to Lu produced by the integrated target-ion source unit have been measured at a temperature of 2500 ^°C. The results of the integrated target-ion source unit use for on-line laser resonance ionisation spectroscopy study of neutron-deficient Gd isotopes have been also presented.     

Multidirmensional gas chromatography – isotope ratio mass spectrometry (MDGC-IRMS). Part A: System description and technical requirements

A system is presented which combines multidimensional GC with isotope ratio mass spectrometry. The performance of the system is demonstrated with an application from the field of flavor analysis. Potentials and limitations of the technique are also discussed.     

On the composition-dependent isotope effect of HTSC in the two-band model

The oxygen isotope effect in high-T_C superconductors has been investigated on the basis of a two-band model where superconducting phase transition is induced by interband (mainly Coulombic) interaction. The isotope shift of T_C appears due to the dependence of averaged interband electronphonon coupling constant on oxygen mass. This coupling has a repulsive nature and gives a relatively small contribution to the total interaction inducing superconductivity. The calculated isotope effect exponent depending on the carrier concentration has been compared with the experimental one as a function of x for La_2-xSr_xCuO₄.     

Stable carbon isotope ratios of methyl-branched fatty acids are different to those of straight-chain fatty acids in dairy products

Methyl-branched fatty acids (MBFAs) are the dominant form of fatty acid found in many bacteria. They are also found at low levels in a range of foodstuffs, where their presence has been linked to bacterial sources. In this study we evaluated the potential of compound-specific isotope analysis to obtain insights into the stable carbon isotope ratios (δ¹³C values in ‰) of individual MBFAs and to compare them to the stable carbon isotope ratios of straight-chain fatty acids in food. Due to their low abundance in foodstuffs, the MBFAs were enriched prior to gas chromatography coupled to isotope ratio mass spectrometric (GC–IRMS) analysis. After transesterification, urea complexation was used to suppress the 16:0 and 18:0 methyl esters that were dominant in the samples. Following that, silver-ion high performance liquid chromatography was used to separate the saturated from the unsaturated fatty acids. The resulting solutions of saturated fatty acids obtained from suet, goat’s milk, butter, and human milk were studied by GC–IRMS. The δ¹³C values of fatty acids with 12–17 carbons ranged from −25.4‰ to −37.6‰. In all samples, MBFAs were most depleted in carbon-13, followed by the odd-chain fatty acids 15:0 and 17:0. 14:0 and 16:0 contained the highest proportions of carbon-13. The results from this study illustrate that MBFAs have distinctive δ¹³C values and must originate from other sources and/or from very different substrates. These measurements support the initial hypothesis that δ¹³C values can be used to attribute MBFAs to particular sources.