The influence of structural defects on the adsorption of simple molecules (H2, C2H2, C2H4, C2H6, CO,NO) on rhenium single crystals

Using Thermal Programmed Desorption (TPD), Low Energy Electron Diffraction (LEED) and Auger Electron Spectroscopy (AES) we have studied the adsorption of hydrogen-containing molecules (H₂, C₂H₂, C₂H₄, C₂H₆) and oxygen-containing molecules (CO and NO) on two vicinal planes of the Re(0001) surface. The two surfaces are designated thus: ReS ¦14(0001)(101̄1)¦, ReS |6(0001)(167̄1) | . The structural defects have little effect on the adsorption of hydrogen and the hydrocarbons. They are more influential in the case of the oxygen-containing molecules. This is particularly true for CO; on the kink sites the CO molecules can completely dissociate whereas only a partial dissociation is possible on the steps. These results should be viewed in relation to the strong bond energy between carbon and oxygen in a CO molecule of 256 kcal/mole and the great affinity of oxygen for rhenium; E_Re?O = 127 kcal/mole.     

Ionization by H+2. Molecular effect

The molecular effect in the ionization of inner shell electrons of aluminum atoms by energetic H⁺₂ molecules has been calculated. We distinguish between the molecular effect in Al and Al₂O₃. We conclude that in the case of Al the protons of the cluster have a definite orientation but in the case of Al₂O₃ the orientation is at random.     

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

使用配有团簇产生和化学反应源的飞行时间质谱装置,研究了锆氧阴离子团簇Zr_xOy^-与乙烷和丁烷的反应. 在反应中发现了Zr₂O₅H^-和Zr₃O₇H^-产物. 用密度泛函理论研究了乙烷在Zr₂O₅^-上的反应通道,发现乙烷脱氢反应可以发生,从而证明观察到的产物是源于脱氢反应. 该工作揭示了锆氧负离子团簇与烷烃反应中的新通道.     

H+5团簇离子及其中性团簇产物H3和H4

报道了H⁺₅的实验结果.分析讨论了H⁺₅的 形成和分解途径.根据理论分析，以稳定的H⁺₃为核心与一个或多个氢分子结合可能形成稳定的H^{+_n氢团簇离子.另一方面，在高频离子源中, 有发生H+₃与H₂反应的条件.实 验中，从高频离子源引出的离子束被静电加速器加速，然后用9 关键词： +}₅团簇离子')" href="#">H⁺₅团簇离子 3中性团簇')" href="#">H₃中性团簇 4中性团簇')" href="#">H_{4中性团簇}     

Carbon-13 Isotopic Species of H2C3, H2C4, and H2C5: High-Resolution Rotational Spectra

The microwave rotational spectra of the carbon-13 isotopic species of H₂C₃, H₂C₄, and H₂C₅ have been observed in a pulsed supersonic molecular beam by Fourier transform microwave spectroscopy. At high resolution all of the rotational lines exhibit hyperfine structure produced by the magnetic interaction between the nuclear spin of ¹³C and the overall rotation of the molecule. The component of the nuclear spin-rotation tensor along the a-inertial axis is large for most isotopic species, especially at the carbene carbon; at this position C_aa is two to three times larger than at other substituted positions along the chain. In contrast to both H₂C₃ and H₂C₃, in H₂C₄C_aa exhibits a pronounced alternation along the carbon chain backbone. Following detection of the five carbon-13 isotopic species and D₂C₅, an experimental structure (r₀) has been determined to high accuracy for H₂C₅.     

Penning ionization electron spectroscopy of H2O,D2O,H2S and SO2

Electron energy peak shifts and peak shapes were determined in the ionization of H₂O, D₂O, H₂S and SO₂ by Ne(³P₂) and He(2¹S, 2³S) metastable atoms. The shifts are large, especially in ionization of H₂O and D₂O into the ionic ground state and are probably mostly due to chemical interaction during the collision.In a previous paper the electron energy distribution curves for ionization of CO, HCl, HBr, N₂O, NO₂, CO₂, COS and CS₂ by helium, neon and argon metastables and the characteristics of this ionization were described¹. In this paper the series of triatomic molecules was extended to the molecules H₂O, D₂O, H₂S and SO₂. Because all these molecules have considerable dipole moments it could be expected that the peak shifts might be enhanced as compared with other triatomic molecules.     

Indication from NMR of Grotthuss mechanism for proton conduction in H2Sb4O11·nH2O

We have measured the second moment, the linewidth and the relaxation times T₁ and T₂ of the ¹H magnetic resonance signal from 4.2 to 380 K in the fact proton conductors H₂Sb₄O₁₁·nH₂O. Our results reveal that the high ionic conductivity of these materials is due to a Grotthuss-type proton diffusion mechanism with succession of molecular reorientations of H₃O⁺ ions or H₂O molecules and of proton jumps from H₃O⁺ to H₂O.     

Rotation-vibration energy cluster formation in XH2D and XHD2 molecules (X = Bi, P, and Sb)

We investigate theoretically the energy cluster formation in highly excited rotational states of several pyramidal XH₂D and XHD₂ molecules (X = Bi, P, and Sb) by calculating, in a variational approach, the rotational energy levels in the vibrational ground states of these species for J?70. We show that at high J the calculated energy levels of the di-deuterated species XHD₂ exhibit distinct fourfold cluster patterns highly similar to those observed for H₂X molecules. We conclude from eigenfunction analysis that in the energy cluster states, the XHD₂ molecule rotates about a so-called localization axis which is approximately parallel to one of the X-D bonds. For the mono-deuterated XH₂D isotopologues, the rotational spectra are found to have a simple rigid-rotor structure with twofold clusters.     

Improved infrared and visible emission spectra of the H3 and D3 molecules

Better-resolved Rydberg-Rydberg emission spectra of the neutral H₃ and D₃ molecules in the infrared and visible regions, with less interference from H₂ and D₂ emission, have been obtained by using a Droege-Engelking type of corona discharge source. Using nl_λ notation, the lower electronic states are 3p₁ in the infrared and 2p₀ in the visible, and the upper electronic states are mixed (3s,3p₀,3d₀,3d₁,3d₂) states. In particular, a line near 16 842 cm⁻¹ in H₃, previously obscured by an H₂ line, reveals a (3s,3d) interaction that is confirmed by other lines. The spectra are analysed including this interaction. However, fits to effective Hamiltonians still have relatively large standard deviations, probably partly due to poor convergence of the rotational expansions and partly due to many small perturbations of the levels by background states.     

钇覆盖Si@Al12团簇的贮氢性能

利用密度泛函理论系统地研究了Y_mSi@Al₁₂ (m=1—3)团簇及其贮氢性质. 结果表明, 在所研究的尺度范围内, 钇原子未在Si@Al₁₂团簇上团聚; 每个钇原子按18电子规则吸附氢分子, 其中Y₃Si@Al₁₂团簇可以吸附16个完整氢分子, 贮氢质量分数为5.0 %, 平均吸附能处于0.324—0.527 eV之间, 较为理想的吸附能说明在室温条件下吸氢和脱氢是可行的.