The calculation of frequency-dependent hyperpolarizabilities including electron correlation effects

The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation.     

Mössbauer spectroscopic study of Prussian Blue from different provenances

Ferric ferrocyanides synthesized from different sources of ferric cations and ferrocyanide anions and those derived from ferrous ferricyanide, ferrous ferrocyanide and ferric ferricyanide have been studied using Mössbauer and XRD techniques. Structural information of the effect of the provenance on the properties of the final compound is obtained. Significant correlations between isomer shift and quadrupole splitting of inner and outer iron cations have been observed.     

The behavior of cracked cross-ply composite laminates under shear loading

An interlaminar-shear-stress analysis developed earlier by Tsai et al. (1990, Micro-cracking-Induced Damage in Composites) for a [φ_m/θ_n], bi-directional composite laminate is used to solve the case of a cross-ply [0_m/90_n]_x laminate with the 90° layer only or both layers cracked under pure shear loading. Strains, forces and laminate shear modulus reduction due to matrix cracking were obtained. Experimental results for shear modulus as a function of crack densities were obtained by a simple shear test and they agree very well with the theoretical prediction.     

Uniformization and the diversity of Whitehead groups

Techniques of uniformization are used to prove that it is not consistent that the Whitehead groups of cardinality ℵ₁ are exactly the strongly ℵ₁-free groups. Some consequences of the assumption that every strongly ℵ₁-free group of cardinality ℵ₁ is Whitehead are derived. Other results about uniformization are also proved. Research partially supported by NSERC grant #9848. Research partially supported by the BSF. The authors thank Rutgers University for its support. Publication #441.     

Ein Verfahren zur Synthese enantiomerenreiner Alkanole durch reduktive Entschwefelung von Thiophenalkoholen

Summary Acetals3 and4 of alkylthienylcarbinols1 were prepared using an enantiomerically pure lactol2. In the key step these compounds were desulfurized. After deprotection the target compounds7 andent-7 were obtained.

Herrn Prof. Dr. H. Oelschläger zum 70. Geburtstag gewidmet     

Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO₃, and the reduced organic sulphur compounds CH₃CH₂SH, (CH₃CH₂)₂S, (CH₃CH₂)₂S₂, and CH₃CH₂SCH₃ in air. The products CH₃CH₂SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₃CH₂ONO₂ were identified and quantified in the reactions of the first three compounds, CH₃CH₂SH, (CH₃CH₂)₂S, and (CH₃CH₂)₂S₂. The reaction products were CH₃CH₂SO₃H, CH₃SO₃H, SO₂, H₂SO₄, CH₃CHO, and CH₂O in the reaction of CH₃CH₂SCH₃. On the basis of identified reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO₃ radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH₃SCH₃, CH₃SH, and CH₃SSCH₃ lead to the conclusion that all these species, in the reaction with the NO₃ radical, follow a similar degradation mechanism producing SO₂, H₂SO₄, R? SO₃H, R? CHO, and R? CH₂ONO₂, as the main reaction products. The inital step of the reaction of NO₃ with R? S? R and R? S? H type (R = CH₃, CH₂CH₃) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct. For the reaction between NO₃ and R? S? S? R type compounds, evidence for an addition-decomposition reaction, as the initial steps, was obtained. R? S·, R? S(O)·, and R? S(O)₂· appear to be formed as intermediates in all the reactions. © John Wiley & Sons, Inc.     

Rapid magnetization reversal in magnetic small particles induced by non-static bias field

Magnetization reversal processes by a switching field in single-domain nano-sized magnetic particles in the presence of a small transverse non-static bias field are studied. Applying an oscillating bias field instead of a static field, the reversal time becomes much shorter when the switching field is slightly stronger than the effective anisotropy field. A pulsed bias field of a suitably chosen duration in the nanosecond scale is found to induce a rapid switching, even when the switching field is smaller than the anisotropy field. The dependence of the reversal time on the frequency of an oscillating bias field and the duration of a pulsed bias field are studied. The present work thus complement the earlier studies on switching in the presence of a static bias field.