Ab initio predictions of zeolite structures and Si NMR chemical shifts

A recent shell-model potential parameterized on ab initio data is used for predicting the all-silica structures of zeolites MFI, MEI, MTW, TON, FAU and of α-quartz. Cluster models are defined around each site and the ²⁹Si NMR shielding constants are calculated by ab initio techniques (GIAO-HF). Good agreement with observed ²⁹Si NMR chemical shifts is found. Comparison is made with shifts calculated for observed structures. The structures predicted by the ab initio shell-model potential prove as accurate as the observed ones when judged on the quality of the calculated ²⁹Si NMR spectra.     

Measurement of the transverse Doppler shift using a stored relativistic7Li+ ion beam

We have performed for the first time precision spectroscopy on a coasting fast⁷Li⁺ ion beam in a storage ring. The ion beam moving with 6.4% speed of light was first electron cooled and then merged with two counterpropagating laser beams acting on two different hyperfine transitions sharing a common upper level (λ-system). One laser was frequency locked to thea ₃ ¹²⁷J₂ hfs frequency component established as a secondary frequency standard at 514 nm. The second laser was tuned over theλ-resonance, which was recorded relative to¹²⁷J₂ hfs components. This experiment is sensitive to the time dilation in fast moving frames and will lead to new limits for the verification of special relatively. The present status of the experiment and perspectives in accuracy are discussed.     

An investigation of the 2D attractive Hubbard model

We present an investigation of the 2D attractive Hubbard model, considered as an effective model relevant to superconductivity in strongly interacting electron systems. We use both hybrid Monte-Carlo simulations and existing hopping parameter expansions to explore the low temperature domain. The increase of the static S-wave pair correlation with decreasing temperature, which depends weakly on the band filling in the explored temperature range, is analyzed in terms of an expected Kosterlitz-Thouless superconducting transition. Using both our data and previously published results, we show that the evidence for this transition is weak: If it exists, its temperature is very low. The number of unpaired electrons remains nearly constant with temperature at fixed attractive potential strength. In contrast, the static magnetic susceptibility decreases fast with temperature, and cannot be related only to pair formation. We introduce a method by which the Padé approximants of the existing series for the susceptibility give sensible results down to rather low temperature region, as shown by comparison with our numerical data. Received: 30 October 1996 / Revised: 23 October 1997 / Accepted: 29 January 1998     

The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

Thermal conductivity and specific heat of amorphous Zr0.67Ni0.33 after structural relaxation

Low-temperature measurements of the thermal conductivity (0.3KT5K) and of the specific heatC (0.07KT3.5K) of splat-cooled amorphous superconducting Zr_0.67Ni_0.33(T _c 2.7K) after different annealing stages are reported. increases progressively (up to 55%) after annealing. An analysis of with the help of normal-state measurements belowT _c in an overcritical field shows that the phonon-electron scattering remains unaltered after annealing. Hence the increase in must be entirely attributed to structure-induced (intrinsic) scattering, i.e. by two-level tunneling states (TLS) at low temperatures (T1K). The specific heat shows a small decrease aboveT _c (by 8%) which is attributed to a small diminution of the electronic density of states at the Fermi level and to a small increase in the Debye temperature. ForTT _c where TLS dominate, the specific heatC decreases less upon annealing than expected from the increase of in the standard tunneling model. This points to a change in the TLS relaxation time spectrum upon annealing, as observed previously for Zr _x Cu_1–x glasses.     

Revised analysis of the structure of the v1 band of methane

The CARS spectrum of the v₁ band of ₁₂CH₄ at a pressure of 14 mbar was recorded using cw excitation in the cavity of a ring argon ion laser. The analysis of the intensity profile of the obarred spectrum led to the detection of inconsistencies with the hitherto proposed calculated positions of transitions with J = 7 to J = 10 and to a relocation of the corresponding lines.