Interpretation of the Vapor Pressure Isotope Effect of BF3

The available experimental data on the vapor pressure isotope effect (VPIE) of BF₃ are interpreted within the framework of the statistical theory of isotope effects in condensed systems. It is shown that the temperature dependence of the VPIE of ¹⁰BF₃/¹¹BF₃ observed by Rayleigh distillation experiments cannot be rationalized at all, while the curie obtained by vapor pressure difference measurements seems to be too steep below the boiling point.     

Solvent-induced H/D isotope effect on129Xe chemical shifts

An effect of substitution of deuterium for protium in molecules of 17 solvents on^l29Xe NMR shifts was studied. The variation range of solvent-induced isotope xenon shifts σ _s ⁱ exceeds 5 ppm and lies in the range from ?1.18 ppm (in CH₃OD solution) to 3.92 ppm (in D₂O) at 28°C. Experimental results agree with the concept that interaction of xenon atoms with solvent molecules is determined predominantly by dispersion forces. Correlations of σ _s ⁱ with the isotope effect on polarizability, boiling point, and vapor pressure of solvents were established. Anomalous manifestation of properties of aqueous solution was detected.     

Direct ab initio dynamics study of rate constants and kinetic isotope effects for C2(A3Π u ) + CH3OH reaction

The hydrogen abstraction of CH₃OH by C₂ (A³Π _u ) has been investigated by direct ab initio dynamics over a wide temperature range 200–3000?K. The potential energy surfaces (PESs) have been constructed at the UCCSD(T)/aug-cc-pVTZ//UMP2/6-311++G(d,p) levels of theory. Two different hydrogen abstractions on the methyl and hydroxyl sites of methanol are considered. For the methyl H-abstraction, it is essentially a hydrogen atom transfer (HAT), whereas the hydroxyl site H-abstraction is better described as a proton coupled electron transfer (PCET) according to the Natural Bond Orbital (NBO) analysis. The results suggest that the methyl site reaction is dominant, and the calculated rate constants are roughly consistent with available experimental values. On the other hand, the temperature dependence of deuterium kinetic isotope effects (KIEs) analysis reveals a substantial normal isotope effect in the methyl H-abstraction process, while normal and inverse KIEs coexist in the hydroxyl H-abstraction channel. Furthermore, the three and four–parameter expressions of Arrhenius rate constants are also provided within 200–3000?K.     

Cross sections for rotational excitation in He－H2 collisions

Close coupling calculations have been carried out for rotational excitations in He－H₂ collisions with symmetric isotopic substitution (He－H₂, D₂, T₂) and asymmetric isotopic substitution (He－HD, HT, DT). Cross sections have been obtained at the incidence energy of 0.3eV. Based on the calculations, the effect of isotopic substitution on atom－diatom collisions is discussed.     

3He(4He)与H2分子碰撞的同位素效应研究

用公认精确度较高的密耦近似方法计算了入射能量E=05eV时惰性气体原子³He(⁴He)与H₂分子替代碰撞体系的转动激发碰撞截面.通过分析³He(⁴He)-H₂碰撞体系分波截面和微分截面的差异,总结出在氦原子的同位素替代情形下³He(⁴He)-H₂碰撞体系分波截面和微分截面随分波数增加和同位素原子质量改变的变化规律. 关键词： 散射截面 密耦方法 同位素替代 散射角     

Anilinolysis of O‐butyl phenyl phosphonochloridothioate in acetonitrile: Synthesis,characterization, kinetic study,and reaction mechanism

This paper describes a simple optimized method for the synthesis of O‐butyl phenyl phosphonochloridothioate ( 4 ) under mild conditions. The target compounds were characterized by ¹H‐nuclear magnetic resonance (NMR), ¹³C‐NMR, and ³¹P‐NMR spectroscopy, as well as mass spectroscopy. The apparent structure of 4 was confirmed by optimization using the B3LYP/6‐311 + G(d,p) level in the Gaussian 09 program in acetonitrile. The nucleophilic substitution reactions of 4 with X‐anilines (XC₆H₄NH₂) and deuterated X‐anilines (XC₆H₄ND₂) were investigated kinetically in acetonitrile at 55.0°C. The free energy relationship with X in the anilines looked biphasic concave upwards with a break region between X = H and X = 3‐MeO, giving large negative ρ_X and small positive β_X values. The deuterium kinetic isotope effects were secondary inverse (k_H/k_D < 1: 0.789‐0.995) and the magnitudes, (k_H/k_D), increased when the nucleophiles were changed from weakly basic to strongly basic anilines. A concerted S_N2 mechanism is proposed on the basis of the selectivity parameters and the variation trend of the deuterium kinetic isotope effects with X.     

Nitrogen-15 Fractionation in the Thermal Decomposition of Nitrous Oxide of Natural Isotopic Composition

Abstract

The ¹⁵N fractionation in the thermal decompostion of nitrous oxide (N₂O) of natural isotopic composition has been investigated in quartz reaction vessel in the temperature interval 888–1073K. The formulas relating the observed experimentally ¹⁵N fractionations with the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p for ¹⁴N¹⁵N¹⁶O, and secondary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_s for ¹⁵N¹⁴N¹⁶O, have been derived. The experimentally estimated ¹⁵N kinetic isotope effects have been compared with the primary and secondary ¹⁵N kinetic isotope effects calculated with the absolute rate theory formulations applied to linear three atom molecules. A good agreement was found for the primary ¹⁵N kinetic isotope effect, (k ¹⁴/k ¹⁵)_p, in the temperature interval 888–1007K. But at 1073K the decompositions of N₂O, accompanied by NO (nitric oxide) formation proceed with a twice times smaller primary kinetic isotope effect, (k ¹⁴/k ¹⁵)_p of 1.0251 ± 0.0009, only, suggesting the nonlinear transition state structures with participation of the fourth external atom at high temperature decompositions of nitrous oxide. The nitrogen isotope effects determined in this study correlate well with nitrogen isotope fractionations observed in the natural biological, earth and atmospheric processes.     

Neutron diffraction study of high-pressure-induced structural changes in the ammonium halogenides ND4Br and ND4Cl

Structural changes in the deuterated ammonium halogenides ND₄Br and ND₄Cl have been studied by neutron time-of-flight diffraction up to pressures of 45 and 35 kbar, respectively. Data on the equations of state and pressure dependence of the deuterium position parameter have been obtained. A comparison with the hydrogen-containing analogs showed that isotopic substitution of deuterium for hydrogen affects only slightly the compressibility of the systems under study, although the effect is noticeable for ND₄Cl. It has been established that the order-disorder transition from the phase with random deuterium distribution (CsCl cubic structure, space group Pm3m) to the ordered phase (same structure, space group ) occurs in both compounds at the same critical value of the position parameter u=0.153±0.002, which is apparently the same for all ammonium halogenides, and, possibly, for other systems of this structural type as well. Fiz. Tverd. Tela (St. Petersburg) 40, 142–146 (January 1998)     

Muonic Molecule Formation in Condensed Deuterium

Resonant formation of the muonic molecule ddμ in dμ atom scattering in condensed deuterium is considered. In particular, ddμ formation in D₂ solid targets containing different ortho-D₂ concentration is discussed, and the respective time spectra of the dd fusion products are shown. The results of the first calculation of the resonant ddμ formation rate in liquid deuterium are presented. At large momentum transfers the ddμ formation rate takes the Doppler form, similar to that obtained for a dilute gas target. A condition of validity of this approximation is also discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simultaneous and sequential adsorption of deuterium and nitrous oxide by rhenium

The addition of nitrous oxide to a stream of deuterium passing over a rhenium filament reduced the initial sticking probability of the latter gas from 0.24 to 0.09 when the proportion of N₂O exceeded 40%. For the addition of deuterium to nitrous oxide the equivalent figures were 0.45 and 0.30 when deuterium exceeded 30% of the gas phase. These results are attributed to a competition between the two gases for places in the precursor state on the surface. The replacement of adsorbed deuterium from a saturated layer by the oxygen atom of nitrous oxide proceeded initially with a high probability, 0.27, at room temperature and with each oxygen atom replacing one deuterium atom. However, the reaction was incomplete, about 2 × 10¹⁴ atoms cm^?2 of deuterium remaining on the surface. It is suggested that kinetic rather than thermodynamic factors are responsible for the incomplete reaction, possibly as the result of a high activation energy for the migration of deuterium atoms over an oxygenated rhenium surface.     

Enhanced superconductivity in zirconium after H(D) implantation

Zirconium foils (superconducting transition atT _c =0.7 K) were implanted at liquid helium temperatures with hydrogen, deuterium and helium. In all cases a remarkable increase ofT _c was observed. Implantation of the inert He atoms leads only to the introduction of lattice defects, which is known to increaseT _c of Zr. However, the implanted H and D atoms exert an additional influence on the superconducting behavior based on a change of the electronic properties and an increase of the electron-phonon coupling. Introduction of lattice defects seems to account for theT _c increase to 1.49 K after He implantation, whereasT _c is even more enhanced by implantation of the hydrogen isotopes. The maximum values forT _c are 3.14 K for H and 4.65 K for D implantation. The concentration necessary to produce a saturation inT _c for both isotopes is H(D)/Zr0.13. The remarkably highT _c for the heavier isotope corresponds to an extreme inverse isotope effect. A smaller inverse isotope effect was found earlier in the Pd –H(D) system, where it could be explained by anharmonic effects.Dedicated to Prof. Dr. W. Buckel on the occasion of his 60th birthday     

Hydrogen isotope replacement reactions on rhenium

The existence of a mobile equilibrium at room temperature between part of the hydrogen adsorbed on rhenium and gaseous hydrogen is demonstrated by the easy exchange of isotopes between the adsorbed layer and the gas phase. The adsorbed gas is desorbed as a mixture of homonuclear molecules (of H₂ or D₂)and of the isotopically mixed species (HD). However, the replacement reactions are not symmetrical; there is a greater proportion of HD in the desorbed gas when deuterium is replaced by hydrogen than in the converse reaction. This kinetic isotope effect is attributed to differences between the zero-point energies of the various hydrogen containing species.Quantatitive agreement between the shapes of the experimentally observed desorption curves and calculated curves is obtained if the zero-point energy of the bond between a surface rhenium atom and deuterium is assigned the value 2.6 kcal mole^?1.     

Muonium formation and the “missing fraction” in vapors

The vapor phase fractional polarizations of positive muons thermalizing as the muonium atom (P _M) and in diamagnetic environments (P _D) has been measured in H₂O, CH₃OH, C₆H₁₄, C₆H₁₂, CCl₄, CHCl₃, CH₂Cl₂ and TMS, in order to compare with the corresponding fractions measured in the condensed phases. There is a marked contrast in every case, with the vapor phase results being largely understandable in terms of a charge exchange/hot atom model. Unlike the situation in the corresponding liquids, there is no permanent lost fraction in the vapor phase in the limit of even moderately high pressures (1 atm); at lower pressures, depolarization is due to hyperfine mixing and is believed to be well understood. For vapor phase CH₃OH, C₆H₁₄, C₆H₁₂, and TMS therelative fractions are found to be pressure dependent, suggesting the importance of termolecular hot atom (or ion) reactions in the slowing down process. For vapor phase H₂O and the chloromethanes, the relative fractions are pressure independent. For CCl₄,P _M=P _D0.5 in the vapor phase vs.P _D=1.0 in the liquid phase; fast thermal reactions of Mu likely contribute significantly to this difference in the liquid phase. For H₂O,P _M 0.9 andP _D0.1 in the vapor phase vs.P _D 0.6 andP _M0.2 in the liquid phase. Water appears to be the one unequivocal case where the basic charge exchange/hot atom model is inappropriate in the condensed phase, suggesting, therefore, that radiation induced spur effects play a major role.     

Vapor Pressure Assisted Void Growth and Cracking of Polymeric Films and Interfaces

Pores and cavities form at filler particle-polymer matrix interfaces, at polymer film-silicon substrate interfaces as well as in molding compounds of IC packages. Moisture diffuses to these voids. During reflow soldering, surface mount plastic encapsulated devices are exposed to temperatures between 210 to 260°C. At these temperatures, the condensed moisture vaporizes. The rapidly expanding water vapor can create internal pressures within the voids that reach 3–6 MPa. These levels are comparable to the yield strengths of epoxy molding compounds and epoxy adhesives, whose glass transition temperatures T _g range between 150 to 300°C. Under the combined action of thermal stress and high vapor pressure (relative to the yield strength at T _g), both pre-existing and newly nucleated voids grow rapidly and coalesce. In extreme situations, vapor pressure alone could drive voids to grow and coalesce unstably causing film rupture, film-substrate interface delamination and cracking of the plastic package.Vapor pressure effects on void growth have been incorporated into Gurson's porous material model and a cohesive law. Crack growth resistance-curve calculations using these models show that high vapor pressure combined with high porosity bring about severe reduction in the fracture toughness. In some cases, high vapor pressure accelerates void growth and coalescence resulting in brittle-like interface delamination. Vapor pressure also contributes a strong tensile mode component to an otherwise shear dominated interface loading. An example of vapor pressure related IC package failure, known as popcorn cracking, is discussed.     

Lattice dynamics and phase diagrams for hydrogen bonded systems

Abstract

A variational correlated ground state wave-function theory is applied to investigate the high-pressure deformation of hydrogen-bond potential described by a double Morse potential functions. The evolution of the hydrogen bond potential with increasing pressure and the effects of deuterium isotope substitution on the quantum-fluctuation-driven phenomena are discussed. The theory was employed for predicting and interpreting the pressure dependence of the phase transition temperatue for KDP-like ferroelectrics and NQR-frequency coefficients for several deuterated and undeuterated crystals.     

用正电子湮没寿命谱研究凝聚态甲烷的温度关系

在30—150K温度范围内,测量了高纯凝聚态甲烷中的正电子寿命谱随温度的变化。在固态甲烷中,正电子素(简称Ps)在自由体积中形成,形成率为²7%。正-正电子素(其符号为o-Ps)的寿命随温度变化的特征可用o-Ps在热激活空位型缺陷中的捕获来说明,且由Ps捕获模型和实验测得的o-Ps寿命求得缺陷激活能E_a=0.10±0.02eV。在液态甲烷中,Ps形成率高达36%,且o-Ps寿命长达5—7ns,这表明液态甲烷中形成了Ps气泡态。我们用经验公式估算了这种气泡的尺寸及其微观表面张力。 关键词：     

载能氢同位素原子与石墨(001)面碰撞的分子动力学研究

采用分子动力学方法研究了载能H同位素原子与石墨晶体碰撞的同位素效应. 碳氢系统的强共价键作用和石墨层间的弱van der Waals力分别用REBO和Ito半经验势函数来描述. 研究发现: 随着入射原子质量的增加, 上表面吸附几率和反射几率的峰值都会向高能区移动; 相比于H, ²H入射原子, ³H入射原子具有较高的吸附几率——包括上表面吸附和内部吸附; 穿透石墨晶体, ²H, ³H原子所需的能量较高; 原子质量和原子入射能量都会影响入射粒子与不同石墨层之间的能量传递过程. 这些结果对理解碳基材料的³H滞留机制有重要意义.     

Investigation of the fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by certain substituted uracils

The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by a series of uracils has been studied in water and acetonitrile solvents using steady-state and time-resolved fluorescence techniques. The steady-state fluorescence quenching technique has been performed in three different pHs (i.e. 4, 8 and 12). The bimolecular quenching rate constant (k_q) increases with increase in pH of uracils. In acidic pH, a pure hydrogen atom abstraction is proposed as the quenching mechanism. This is supported by a pronounced solvent deuterium isotope effect. Electron transfer from the anionic form of uracil to the excited state of DBO is proposed as a mechanism for quenching in basic pH on the basis of highly exergonic thermodynamics obtained from the Rehm-Weller equation. The variation of k_q is explained on the basis of the electronic effect of substitution in uracils as well.     

Deuterium and Oxygen-18 in Surface Waters of GDR draining to the Baltic Sea

A general view is presented of deuterium and ¹⁸O measurements of water samples collected at running and standing surface waters in German Democratic Republic. The values confirm earlier observations that the surface waters are influenced by evaporation with respect to the isotopic composition of groundwater. Nevertheless, stronger evaporation effects are restricted to larger lakes. The amount of surface water discharge from GDR to the Baltic Sea and the δD and δ¹⁸O values are discussed. The river Oder provides about 90% of the whole surface run-off. The other watercourses to the coast are unimportand. The mean heavy isotope content of surface run-off was calculated to be ?8.3‰ for δ¹⁸O and ?61‰ for δD (vs. SMOW), respectively.     

Low-temperature plasticity of pure parahydrogen

Stress-strain curves of single crystals of pure (99.9999 mol%) parahydrogen (p-H₂) were measured in the temperature range 1.8–4.2 K under conditions of stepped uniaxial stretching. The parahydrogen under study has a significantly decreased deuterium (stable isotope) content ([D]/[H] ～ 0.005–0.006 at %) as compared to the natural isotope composition. The deuterium content was decreased using for the first time a method in which parahydrogen was crystallized and then melted and the vapor thus obtained was distilled. It was revealed that the yield stress of the single crystals decreases anomalously as the temperature is decreased. The anomalous behavior indicates a coherent band motion of defects (most likely, dislocation kinks) resulting in low-temperature plasticity of the pure p-H₂ studied.