Direct ab initio dynamics calculations of the reaction rate for the hydrogen abstraction reaction of NCO with CH4 and C2H6

The kinetics of the hydrogen abstraction reactions NCO + CH₄ (R1) and NCO + C₂H₆ (R2) have been studied over a wide temperature range. The minimum energy paths (MEPs) were calculated at the MP2/cc-pVDZ level and single-point calculations were refined at the G3MP2 level. The rate constants for the title reactions were calculated using canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions. The fitted three-parameter formulae are k ₁ = 2.52 × 10^?22 T ^3.46 exp(2466/T) and k ₂ = 9.8 × 10^?22 T ^3.2 exp(411.8/T) cm³ molecule^?1 s^?1 for (R1) and (R2), respectively. The calculated rate constants were found to be in good agreement with the available experimental data. Deuterium kinetic isotope effects were also investigated. Both reactions show a significant kinetic isotope effect in the low-temperature range.     

Dynamics of gas-phase reactions of muonium

Applications of variational transition state theory with semiclassical adiabatic transmission coefficients to the reactions of muonium with H₂, D₂, F₂, and Cl₂ are reviewed. In addition new calculations are presented for the Mu+Cl₂ and Br₂ reactions. The comparison of calculated rate constants and kinetic isotope effects (KIE's) with experiment is used as a test of the validity of semiempirical potential energy surfaces. Furthermore the VTST-plus-tunneling calculations allow an analysis of the KIE's that identifies those features of the potential which control the isotope effects.     

A waveguide reactor for IR multiphoton dissociation and its application to13C laser isotope separation

A waveguide reactor for infrared multiphoton dissociation reactions has been presented and applied to laser isotope separation of¹³C. The reactor is a sealed vessel containing a hollow waveguide for a CO₂ laser, and the laser beam is condensed in the waveguide. The waveguide is a pipe of total-reflection glass or metal-coated glass with a funnelled inlet; it is 50 cm long with a 3 mm inner diameter. The isotope separation of¹³C has been made by multiphoton dissociation of CHF₂Cl using a TEA CO₂ laser. The result has shown that the waveguide reactor increases the dissociation yield by four to ten times as much as that without the waveguide at the pulse rate of up to 150 Hz, while the separation factor remains on the same level. It is also found that an optical breakdown which is induced at the wall surface plays a significant role to reduce the isotope selectivity.This work is for a partial fulfilment of B.S. degree of Osaka Electric Communication University     

Surface photochemistry and photodesorption

Use of light to promote chemical reactions has been studied for a long time. The fact that solar energy is a primary ingredient of all forms of fuel, from combustible materials to wind power (excluding nuclear), together with the impending energy shortage has brought about a resurgence of interest in photochemistry. The development of the laser has resulted in the pursuit of new methods of isotope separation. This paper presents two new applications for light-induced reactions: surface photochemistry and photodesorption. Both are applicable to photochemical synthesis of compounds and separation of chemical or isotope mixtures. Emphasis is given to the more demanding isotope separation aspects of surface photochemistry and photodesorption. Conditions for chemical synthesis or chemical separation are treated as a logical extension of the isotope separation treatment.     

Isotope effect and characteristic features of the phase diagram for cobaltites with spin-state transitions

The effect of ¹⁶O → ¹⁸O oxygen isotope substitution has been studied for (Pr_1−y Eu _y )_0.7Ca_0.3CoO₃ cobaltites (0.12 < y < 0.26). A pronounced isotope shift has been found for the spinstate transition temperature, which increases with the oxygen isotope mass. In contrast, the ferromagnetic transition temperature has slightly lower values for the samples with heavier oxygen. The observed phenomena and constructed phase diagram confirm the results reported previously for (Pr_{1 − y} Sm _y )_0.7Ca_0.3CoO₃ in [G. Y. Wang, X. H. Chen, T. Wu, et al., Phys. Rev. B 74, 165113 (2006)]. The measurements of the specific heat have been performed for (Pr_{1 − y} Eu _y )_0.7Ca_0.3CoO₃ with the main emphasis on the analysis of the isotope effect. The contributions to the isotope effect coming from the lattice and magnetic components of the specific heat have been separated. The mechanisms underlying the large isotope effect are discussed.     

Thermal conductivity of (La0.25Pr0.75)0.7Ca0.3MnO3 under giant isotope effect conditions

The thermal conductivity of (La_0.25Pr_0.75)_0.7Ca_0.3MnO₃ manganite has been studied. The isotope substitution of ¹⁸O for ¹⁶O in this compound leads to a ferromagnetic-antiferromagnetic phase transition at low temperatures. It has been found that the thermal conductivity in the ferromagnetic state is approximately two times higher than in the antiferromagnetic state. It has been shown that the small value of thermal conductivity and its temperature dependence can be due to strong phonon scattering from crystal lattice defects, which are thought of as Jahn-Teller distortions. The parameters of this scattering can be determined within the Debye model of thermal conductivity from a comparison of samples differing in their isotope composition.     

Isotope Effects During Metabolism of (±)-Tramadol Isotopomers by Human Liver Microsomes

Tramadol (T), racemic 1(e)-(m-methoxyphenyl)-2(e)-(dimethylaminomethyl)-cyclohexane-1(a)-ol is an effective analgesic drug. Metabolites were formed by O- and N-demethylation. Six deuterated tramadol isotopomers have been synthesized; their kinetic isotope effects in oxidative demethylation reactions were investigated in vitro using human liver microsomes. In comparison to unlabelled (±)-tramadol, (±)-T-OCD₃ and (±)-T-D₉ displayed an unequivocal (< 3), (±)-T-ND₆ and (±)-T-ND₃ a noticeable, and (±)-T-cyclohexyl-D₃ as well as (±)-T-¹⁵ND₂ no measurable isotope effect. Metabolic switching (favoring the N-demethylation) was observed only after incubation of a tramadol with a trideuterated methoxy group. Additional N-CD₃-groups prevented this metabolic switching. Metabolic switching favoring the O-demethylation was not observed. The isoenzyme responsible for the O-demethylation was always saturated under the experimental conditions required to detect the metabolites.

The two tramadol isotopomers containing deuterium in metabolic inert positions (other than the methyl groups, i.e., (±)-T-¹⁵ND₂ and (±)-T-cyclohexyl-D₃) were expected to display no isotope effects. This expectation could be verified in this study.     

Doubly decoupled bands in176, 178Re

High spin states in^{176, 178}Re have been studied using in-beam γ and e^? spectroscopy techniques through heavy ion induced fusion reactions. A ΔI=2 rotational band of doubly decoupled type has been identified in each isotope.     

35MeV/u40Ar+197Au中的熵产生

根据量子统计模型(QSM)的计算分析,找到了一个提取核反应过程中熵产生的新的可观测量.核反应过程中约化d的产额d/(d+t+³He+⁴He)和熵有单调的函数关系,并且和体系的碎裂密度(ρ/ρ₀)及体系的N/Z都无关,可以作为提取核反应过程中熵产生的一个观测量.和目前已经有的其他方法相比,约化d产额这一提取熵方法可以用于较低能量的重离子核反应中,并且数据处理分析简单.对于35MeV/u⁴⁰Ar+¹⁹⁷Au的核反应过程所提取的熵和利用约化带电粒子多重性提取的熵结果一致.结合后角类靶热核发射体系实验提取的同位素核温度为4.7±1.2MeV及S/A=2.5±0.5,根据熵和核温度的关联关系,可以确定其Break up密度接近但小于0.1(ρ/ρ₀) 关键词： 熵 约化d产额 核温度 统计发射     

Isotopic selectivity of IR laser photodissociation of CF3I molecules

The selectivity dependence of multiphoton dissociation of CF₃I on the conditions of excitation (pulse duration, concentration of the isotope under excitation and gas pressure) has been studied. It has been shown that the main mechanism of selectivity loss isV-V exchange during a laser pulse. The elaborated model is in good agreement with the experiment.     

Multineutron photonuclear reactions on the <Superscript>197</Superscript>Au isotope

An experiment on irradiation of the ¹⁹⁷Au isotope by a beam of bremsstrahlung γ-rays of maximum energy E _γ ^m = 70 MeV has been carried out at the RTM-70 race-track microtron of the INP MSU. Residual activity spectra of the irradiated sample were measured. Multiparticle photonuclear reactions on the ¹⁹⁷Au nucleus are observed. Photonuclear reactions with emission of as many as six neutrons are observed for the first time.     

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite,and the effect of ion (de)solvation

In this study, we present the experimental results for stable barium (Ba) isotope fractionation (¹³⁷Ba/¹³⁴Ba) during the transformation of aragonite (CaCO₃) and gypsum (CaSO₄·2H₂O) in Ba-bearing aqueous solution to witherite (BaCO₃) and barite (BaSO₄), respectively. The process was studied at three temperatures between 4 and 60?°C. In all cases, the transformation leads to a relative enrichment of the lighter ¹³⁴Ba isotope in the solid compared to the aqueous solution, with ^137/134Ba enrichment factors between –0.11 and ?0.17?‰ for BaCO₃, and –0.21 and –0.26?‰ for BaSO₄. The corresponding mass-dependent ^138/134Ba enrichment factors are ?0.15 to –0.23?‰ for BaCO₃, and –0.28 to –0.35?‰ for BaSO₄. The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80?°C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO₄ and BaCO₃ using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.     

Nuclear moments and charge radii of107–111in determined by laser spectroscopy

Collinear fast beam laser spectroscopy has been used to measure the hyperfine structure and isotope shift in the atomic 5s ² 5p ² P _3/2-5s ² 6s ² S _1/2 transition (λ=451 nm) of^107–111In. Secondary beams of neutron deficient indium isotopes were prepared at the GSI on-line mass separator following fusion evaporation reactions. Magnetic dipole moments and electric quadrupole moments have been determined. The isotope shifts are discussed in terms of the change of the mean square nuclear charge radii and compared with the droplet model predictions and the deformation values calculated from the quadrupole moments.     

Stable Carbon Isotope Fractionation in Lower Plants from the Schirmacher and Untersee Oases (Central Dronning Maud Land,East Antarctica)

Abstract

Lower plants (algae, lichens, mosses) from the Antarctic continent have been analysed for their stable carbon isotope composition. In contrast to lichens and mosses which exhibit quite normal δ¹³C-values the studied microbial benthos is characterized by an extremely low carbon isotope fractionation (δ¹³C-values up to ?1.4‰. vs. PDB). Limited CO₂ availability and bicarbonate uptake are probably the main factors responsible for this phenomenon.     

Optical Tomograms of Multiple-Photon-Added Gaussian States via the Intermediate State Representation Theory

The oxygen isotope effect in PrBaMn₂^16-18 O_5.97 manganite with an ordered cation arrangement is studied. The field dependences of magnetic susceptibility and magnetization are measured in the temperature range 100–270 K and magnetic fields up to 32 T. A significant increase in the temperature of the spin-reorientation antiferromagnet–ferromagnet phase transition is detected in samples enriched in heavy oxygen ¹⁸O (negative isotope effect). The transition temperature and the isotope effect depend strongly on the magnetic field. An H–T phase diagram is plotted for samples with various isotope compositions. An analysis of the experimental results demonstrates that the detected negative isotope effect and the giant positive isotope effect revealed earlier in doped manganites have the same nature. The mechanisms of appearance of isotope effects are discussed in terms of the double exchange model under a polaron narrowing of the free carrier band.     

Thermal chemistry of diiodomethane on Ni(1 1 0) surfaces I. Clean and hydrogen-covered

The thermal chemistry of diiodomethane on Ni(1 1 0) single-crystal surfaces was studied by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Diiodomethane was chosen as a precursor for the formation of methylene surface species. I 3d and C 1s XPS data indicated that, indeed, adsorbed diiodomethane undergoes the C-I bond dissociations needed for that transformation, and detection of iodomethane production in TPD experiments pointed to the stepwise nature of those reactions. Significant amounts of methane are produced from further thermal activation of the chemisorbed methylene groups. This involves surface hydrogen, both coadsorbed from background gases and produced by dehydrogenation of some of the adsorbed diiodomethane, and can be induced at temperatures as low as about 160 K, right after the C-I bond breaking steps. Unique to this system is the detection of significant amounts, up to 10% of the total CH₂I₂ adsorbed, of heavier hydrocarbons, including ethene, ethane, propene, propane, and butene. Deuterium labeling experiments were used to provide support for a mechanism where the initial hydrogenation of some adsorbed methylene to methyl moieties is followed by a rate-limiting methylene insertion step to yield ethyl intermediates. Facile subsequent β-hydride elimination and reductive elimination with coadsorbed hydrogen account for the formation of ethene and ethane, respectively, while a second and third methylene insertions lead to C₃ and C₄ production. Based on the final product distribution, the methylene insertion was estimated to be approximately 20 times slower than the following hydrogenation-dehydrogenation reactions. Normal kinetic isotope effects were observed for most of the hydrogenation and dehydrogenation reactions involved.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

Hyperfine structure and isotope shift of the neutron-rich barium isotopes139–146Ba and148Ba

The hyperfme structure and isotope shift in the 6s ² S _1/2?6p ²P_3/2 line of Ba II (455.4 nm) have been measured by collinear fast-beam laser spectroscopy for the neutron-rich isotopes^139–146Ba and¹⁴⁸Ba. Nuclear moments and mean square charge radii of these isotopes have been recalculated. The isotope shift of the isotope¹⁴⁸Ba (T_1/2=0.64 s) could be studied for the first time, yieldingδ〈r²〉^138,148=1.245(3) fm².     

Reactions of excited atoms and molecules with atoms and molecules

Ionizing collisions of long lived excited particles with atoms and molecules are studied by a cross beam technique. For the first time reactions of atoms in high Rydberg states are included in the investigation. In this paper we report relative cross sections for the production of the ions RH⁺, RH ₂ ⁺ , and H ₂ ⁺ by collisions of excited rare gas atoms R^* with H₂. With HD as the target molecule the isotope effect for the production of RD⁺ and RH⁺ has been determined. In the case of argon and krypton, ions are produced only by the high Rydberg states, whereas in the case of helium and neon only the metastable states contribute to a measurable extent. The data indicate, that the reaction mechanism is different in principle for metastable and highly excited atoms. Simple models are proposed to explain the experimental results.