Chemical-Shifts in Magnetic-Resonance of the 3He Nucleus in Liquid Solvents and Comparison with Other Noble Gases

Gas-to-solution solvent shifts of ³He dissolved in 17 pure liquids were measured. Two types of samples were used, under helium pressures of about 2 and 30 atm. No measurable pressure effect on the shift could be detected. The gas-to-solution shifts are dominated by the bulk susceptibility, for which correction was made. The resulting medium-shift range in our solvents is about 0.8 ppm. Hence ³He provides an excellent probe for the detection of minute local magnetic fields at the site of noble-gas atoms. For the first time shifts in liquid solvents for all four NMR-accessible noble-gas nuclei (³He, ²¹Ne, ⁸³Kr, and ¹²⁹Xe) can be compared. The medium shifts of ³He show a roughly linear correlation to medium shifts of ¹²⁹Xe, ⁸³Kr, and ²¹Ne in the same solvents. The corrected relative solvent shifts, that is, the solvent effects divided by σ_d, the diamagnetic shielding of the free atom, and by the number of nearest-neighbor solvent molecules, are approximately equal for all four noble gases.     

Spectral anomalies of the light-induced drift of rubidium atoms caused by the velocity dependence of transport collision frequencies

The spectral features of the light-induced drift (LID) velocity for rubidium atoms (⁸⁵Rb and ⁸⁷Rb) in an argon buffer medium and in binary buffer mixtures of noble gases (Ne + Ar, Ne + Kr, Ne + Xe, He + Ar, He + Kr, and He + Xe) have been investigated theoretically. A strong temperature dependence of the spectral shape of the LID signal for Rb atoms in an Ar atmosphere is predicted in the temperature range 450 K < T < 800 K. It is shown that the anomalous LID of Rb atoms in binary buffer mixtures of noble gases can be observed at almost any temperature (including the room one) depending on the fractions of neon or helium in these mixtures. The results obtained enable a highly accurate testing of the interatomic interaction potentials used to calculate the drift velocity for anomalous LID in LID experiments.     

NMR spin-lattice relaxation of the129Xe nucleus of xenon gas dissolved in various isotropic liquids

The spin-lattice relaxation time of the¹²⁹Xe nucleus of natural xenon gas dissolved in various isotropic liquids, acetonitrile, benzene, carbon tetrachloride and cyclohexane, was studied as a function of temperature at the magnetic fields of 9.4 and 4.7 T. The utilization of hydrogenated and deuterated benzene and cyclohexane reveals that the intermolecular¹²⁹Xe-¹H dipole-dipole interaction constitutes an important relaxation mechanism in hydrogenated solvents. According to this interpretation the interaction is rather strongly temperature-dependent, and increases with increasing temperature. An important observation of an experimental nature is also noted, namely convective flow present in non-spinning sample tubes at elevated temperatures disturbs inversion-recovery measurements and leads to erroneous and unreliable relaxation time values.     

Molecular dynamics simulations of quadrupolar relaxation of 131Xe in carbon tetrachloride,acetonitrile, and methanol

The nuclear relaxation of ¹³¹Xe in different solvents (carbon tetrachloride, acetonitrile and methanol) has been studied by means of molecular dynamics simulations. The solvation structure around xenon is examined with radial and angular distribution functions. Electric field gradient time correlation functions (EFG-TCF) have been calculated for the electric field gradient at the site of xenon, and are discussed in terms of molecular self- and cross-correlations. The amplitudes of total EFG-TCF for acetonitrile are comparable for the two potentials, a 3-site and a 6-site model, although the self- and cross-correlation EFG-TCF differ significantly between the models. For all solvents, the simulations give quadrupolar relaxation rates close to the experimental results.     

Na 32P-32D line broadening by Ne,Ar, and Xe

The normalized emission intensity in the wings of the optically thin Na 3²P-3²D lines broadened by Ne, Ar, and Xe has been measured in emission from a high-pressure discharge. A blended satellite occurs about 80 cm^-1 into the Na-Xe red wing and a progression of increasing red wing intensity from Ne to Ar to Xe is observed. Xe densities of 2.5 and 9.1 × 10¹⁹ cm^-3 were used, and the pressure dependence of the NaXe line shape indicates that multiple perturber interactions are important in the far wing at the higher noble gas densities.     

Experimental evaluation of the gas-phase collision cross-section of effusive Au beam with noble gases: The effect of size and flux

We find that the effusive atomic beam of Au atoms is deflected away by collision with noble gas atoms crossing in a perpendicular geometry with a beam flux of >1 × 10¹⁶/cm²s. The ratio of defected Au atoms is found to increase proportional to the flux of noble gases. In addition, the effective cross-section for the collision between Au and noble gases (Ne, Ar, Xe) is measured to increase in an order of Ne < Ar < Xe. As a result of the increased collision probability, the deflection ratio of Au beam in the noble gases is measured to be enhanced for the Au flux in the range of 1 × 10¹¹–10¹³ Au/cm²s. Our results show that the gas-phase collision can be reliably determined by measuring the deflection ratio. The experimentally determined collision cross-section also explains the variation in the deflection ratio among various noble gases and the importance of a long-range van der Waals interaction between Au and noble gases in the deflection efficiency.     

Spin relaxation of the8 S 7/2 ground state of europium in noble gases

Spin relaxation of the 4f ⁷ 6s ^{2 8} S _7/2 ground state of the Eu atom in noble gases was investigated by the direct, continuous optical pumping method. Transient signals could be observed by pulsed saturation of rf Zeeman transitions within theF= 6 hfs level of the stable Eu isotopes. The time constant of the transient signals can be related to the electronic spin depolarization cross section for Eu-noble gas collisions, yielding noble gas He Ne Ar Kr Xe σ₁in 10^?20 cm² 0.99(10) 5.1(5) 15(1.5) 43(4) 97(10) These cross sections exceed those measured forS-states of alkalies by three orders of magnitude. They can be explained by perturbations of theS-ground state configuration of Eu due to the admixture of excited state non-spherical wave functions.     

Isotopic thermal diffusion factors of the noble gases

A new set of isotopic thermal diffusion factors for Ar, Kr and Xe is reported. The data have been obtained from thermal diffusion column measurements in a column previously calibrated with Ne gas, and complete the α_T data for the binary mixtures of noble gases given previously. The results lead to the conclusion that the thermal diffusion properties of the noble gases and their mixtures are well described by the law of corresponding states first proposed by Kestin, Ro and Wakeham. It is also concluded that the calibration technique used makes the thermal diffusion column a valuable instrument for the determination of the thermal diffusion factors of isotopic and non-isotopic dilute gas mixtures.     

Reaction field model with free volume for the NMR chemical shift of129Xe dissolved in organic solvents

The temperature dependence of the NMR chemical shift of¹²⁹Xe dissolved in liquid alkanes is examined in the context of the reaction field model. An essential feature of the theory is the inclusion of the temperature dependence of the density of thesolvent. The theory of free volume for liquids is incorporated into the reaction field model to account for this temperature dependence. Comparison of the theory with previously reported measurements indicates the sensitivity of the¹²⁹Xe chemical shift to the free volume of liquids. Incorporation of free volume improves the agreement between measurement and theory for branched alkane solvents, and resolves the origin of the 62 ppm intercept in the plot of reaction field as a function of¹²⁹Xe chemical shift for the n-alkanes.     

Optical pumping of ions in buffer gases

Transient signals measured with a pulsed rf-optical pumping method are used to determine longitudinal relaxation rates for Sr⁺ ions (even isotopes) in noble gas buffers. Depolarization cross sections of the electronic spin in the Sr⁺5² S _1/2 ground state for binary collisions with rare gas atoms are deduced. The results for σ(Sr⁺5² S _1/2) in Ų are (at temperatures between 374 and 449 °K): 2·10^?5(He),4·10^?5(Ne), 5.7·10^?3(Ar), 1.8·10^?2(Kr), and 4.0·10^?2(Xe). These cross sections for the Sr⁺ ion are about two to three orders of magnitude larger than the corresponding ones for the isoelectronic neutral Rb atom. The large increase of the Sr⁺ relaxation rates is explained with the relaxation mechanism of spin-orbit coupling, taking into account two “indirect” effects of the ionic charge: the increase in the gas kinetic cross sections and the more intimate collisions of the Sr⁺ ion with the noble gas atoms. The depolarization is shown to be predominantly due to short-range interactions. A contribution to the relaxation of the Sr⁺ ion from Sr⁺-noble gas molecule formation, induced by three-body or resonant two-body collisions, could not be established for applied pressuresp between 1.5 and 15 Torr of Ar, Kr, and Xe.     

Hyperpolarized (131)Xe NMR spectroscopy

Hyperpolarized (hp) (131)Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T(1) relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent (131)Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in (129)Xe SEOP. (131)Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase (131)Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp (131)Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp (131)Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I ≥ 1/2 nuclei is presented.     

Messung der Wirkungsquerschnitte für die Linienverbreiterung von Hochfrequenzübergängen im 63 P 2-Zustand des Quecksilbers durch Stöße mit Edelgasatomen

The linewidth of high frequency transitions between Zeeman-levels of the metastable 6³ P ₂-state of mercury is measured as function of the pressure of various noble gases. The measurements are made for all noble gases in the pressure range from 10^?3 to about 2 · 10^?2 Torr. The cross sections for linebroadening due to atomic collisions are derived from the pressure dependence of the linewidth. These cross sections σ were found to be (71 ± 10) · 10^?16 cm² for He, (82 ± 10) · 10^?16 cm² for Ne, (153± 12) × 10^?16 cm² for Ar, (204±28) · 10¹⁶ cm² for Kr and (291 ± 41) · 10^?16 cm² for Xe.     

129Xe and131Xe NMR of xenon on silica surfaces at 77 K

Little is known about¹²⁹Xe NMR spectral features and spin-lattice relaxation behavior, and the dynamics of xenon atoms, for xenon adsorbed on solid surfaces at cryogenic temperatures (≤77 K), where exchange with gas-phase atoms is not a significant complication. We report¹²⁹Xe NMR experiments at 9,4 T that provide such information for xenon adsorbed onto the hydroxylated surface of a number of microporous silica samples at 77 K. A convenient design for these cryogenic experiments is described. Dynamics of surface-adsorbed xenon atoms on the time scale of seconds can be observed by¹²⁹Xe NMR hole-burning experiments; much slower dynamics occurring over hours and days are evidenced from changes with time of the¹²⁹Xe NMR chemical shifts. The peak maxima occur in the region ca. 180–316 ppm, considerably downfield of¹²⁹Xe shifts previously reported on surfaces at higher temperatures, and closer to the shift of xenon bulk solid (316.4±1 ppm). The¹²⁹Xe spin-lattice relaxation timesT ₁ range over five orders of magnitude; possible explanations for both nonexponential relaxation behavior and extremely shortT ₁ values (35 ms) are discussed. Preliminary¹³¹Xe and¹H NMR results are presented, as well as a method for greatly increasing the sensitivity of¹²⁹Xe NMR detection at low temperatures by using closely-spaced trains of rf pulses.     

On spin relaxation of optically pumped cesium vapour

〈S_Z〉 relaxation of cesium is measured in the presence of foreign gases, using the detecting beam method. From the results obtained in the low-pressure regions calculations for the diffusion coefficient, D₀, for cesium in Ne and Ar yield values of 0.113 cm²/sec and 0.145 cm²/sec at 760 torr and 0°C, respectively. A comparison of our D₀ values with those published previously is made.     

Dynamical treatment of binding,polarization and recoil in asymmetric ion-atom collisions

The cross sections for quenching the lowestn ² P states of the alkali atoms Li, Na, K., and Rb by the inert gases He, Ne, Ar, Kr, and Xe are presented for 5 eV≦E _c.m.≦ 100 eV. These cross sections are derived from the corresponding cross sections for collisional excitation by applying the principle of microreversibility. Upper estimates for the quenching cross sections at thermal energies are given; in all studied cases the quenching cross sections are <8·10^?3Ų. These new upper limits are in most cases much lower than those obtained from other methods previously.     

Präzisions-Massenbestimmungen mit dem elektrischen Massenfilter

The construction of an electric quadrupole spectrometer for precision mass determinations in the regionA>130 is described. The hyperbola-shaped electrodes are formed by sets of wires. A method is discussed which reduces the measurement of a mass ratio to a measurement of the ratio of two resistors. In contrast to the conventional ‘peak matching’ technique, in this method the intensity ratio of both members of a dublett occurs as an additional parameter and has to be measured. For testing, measurements were done on Xe-isotopes. The mass ratios obtained are:¹³²Xe/¹³¹Xe=1.007 632 1 ±5,¹³⁴Xe/¹³²Xe=1.015 730. The intensity ratio of¹³²Xe/¹³¹Xe is 0.7872±0.0020. These values are in good agreement with the most accurate measurements of Nier's laboratory.     

A new laser concept for isotopically selective analysis of noble gases

A new laser approach for the isotopically selective analysis of noble gases is presented. This approach uses noble gas atoms prepared in the 1s ⁵ metastable state. Hyperfine levels in the 1s ⁵ and 2p ⁹ states form two-level systems in Ne, Ar, Kr, and Xe which can be excited by a commercially available single-frequency laser system. Absorption of photons from such a laser, and the resulting momentum transfer, can be used to selectively deflect the desired isotope from a supersonic atomic beam into a detection area. Light from the same laser can then be used to selectively count atoms of the desired isotope using the photon-burst technique. Thus, enrichment and selective detection are accomplished with a single laser in a single pass through the apparatus.The problem of analyzing for⁸⁵Kr in a sample of noble gases extracted from the air is examined in detail. This is a stringent test of the selectivity of this approach because⁸⁵Kr has the same nuclear spin, and thus similar hyperfine splittings, as naturally occurring⁸³Kr. Calculations indicate that isotopic selectivity of the new approach is easily adequate to resolve⁸⁵Kr in a 10¹⁰ excess of⁸³Kr.     

Kr/Xe气体在塑料闪烁体表面的吸附与扩散行为研究

采用基于Compass力场的分子动力学(MD)方法,研究了惰性气体氙(Xe)和氪(Kr)在塑料闪烁体(聚乙烯基对甲苯)的平整和粗糙表面的吸附和扩散行为.由惰性气体吸附曲线的均方根位移(MSD),得到了Xe/Kr气体在聚乙烯基对甲苯表面的扩散系数.研究结果表明,Kr/Xe气体均被稳定地吸附在塑料闪烁体表面,其稳定性随着温度的升高而增加,Xe分子的吸附性强于Kr分子. Kr/Xe气体在聚乙烯基对甲苯表面具有较强的扩散性能,扩散深度随着温度与厚度的增加而增加,最大为22.865?,Kr分子扩散能力强于Xe分子.基底粗糙表面增加了两种惰性气体分子的吸附和扩散.     

A comparison of self broadening and shift of helium,neon and argon emission lines

Self broadening (van der Waals and resonance) and shift of Ne emission lines and van der Waals broadening and shift of He emission lines have been measured using a high pressure (0.5–3.0 atom), low current discharge. These results are compared with previous measurements in Ar and He to obtain a complete comparison of self broadening and shift of He, Ne and Ar emission lines. Oscillator strengths for the resonance transitions are obtained from the resonance broadening coefficients. The trend of the van der Waals broadening coefficients for the three noble gases is correctly predicted by a theory due to HINDMARSHet al.⁽⁴⁾ in which a Lennard-Jones potential is used in the impact theory formalism. The measured line shifts cannot be accounted for by this theory and reflect the need for more accurate quantum mechanical calculations.