Thermodynamic properties of ternary semiconducting alloys

Using the new information supplied by extended-x-ray-absorption-fine-structure measurements and the results of our structural model, we compute the bond probability of a few ternary semiconducting III–V and II–VI alloys as a function of temperature and composition in the framework of a modified quasi-chemical approximation. We derive the thermodynamic functions of mixing, considering both elastic and chemical contributions to the bond energies. We examine how the deviation from the full randomness affects the ordering of such alloys and we construct the phase diagrams in the region of phase separation. Possible formation of ordered compounds at low temperatures is predicted.     

Long-Term Cultured Hairy Roots of Chicory—A Rich Source of Hydroxycinnamates and 8-Deoxylactucin Glucoside

Foam fractionation is a promising method for separation and concentration of biochemicals. It is simple, easily scalable, inexpensive, and environment friendly. Foam fractionation thus represents an alternative to the traditional methods used for immunoglobulin enrichment. However, little, if any, literature exists documenting the utilization of foam fractionation in the enrichment of immunoglobulins. Milk were utilized as an immunoglobulin source to serve as examples of a real system in this study. The investigation examined the effects of varying five different process parameters: the initial pH value, the initial concentration of immunoglobulin, the nitrogen flow rate, the column height, and the foaming time. Experimental results demonstrated that immunoglobulin could effectively be enriched from milk by foam fractionation. The maximum enrichment ratio with pretreatment (using pH 4.6 precipitation) was 6.30 along with a more than 92 % recovery for IgG and an enrichment ratio of 5.1 with 85 % recovery for IgM.     

Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers

Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor O? O distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three‐body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical O? O distances are in good agreement. The cooperativity effects revealed by the hydrogen bond O? O distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules.     

A new torsion-rotation fitting program for molecules with a sixfold barrier: Application to the microwave spectrum of toluene

A new program is described for fitting rotation-torsion energy levels in molecules like toluene, in which the frame (C₆H₅) has C_2v symmetry and the methyl top has C_3v symmetry, i.e., for molecules where the internal rotation barrier is expanded in cos6nα, where α is the internal rotation angle and n = 1,2,…. The program is based on the theoretical framework developed by Sørensen and Pedersen in their application of the Longuet-Higgins permutation-inversion group G₁₂ to the microwave spectrum of CH₃NO₂. It is specifically designed for sixfold barrier molecules, and allows the user to select almost any symmetry-allowed torsion-rotation term for inclusion in the fitting Hamiltonian. This program leads to a very successful fit of transitions in the microwave spectrum of toluene characterized by J ? 30, K_a ? 12, and by the free-rotor quantum number ∣m∣ ? 3. In these fits we included both published and rather extensive unpublished new measurements, for which fits using other torsion-rotation programs have not been very successful. The fit presented here uses 28 parameters to give an overall standard deviation of 7.4 kHz for 372 line frequencies, and results in a much improved value for the sixfold barrier for toluene, V₆ = 13.832068(3) cal mol⁻¹.     

The millimeter wave rotational spectrum of pyruvic acid

The rotational spectrum of pyruvic acid has been investigated for the first time in the millimeter-wave region, at 160-314 GHz, and also in supersonic expansion, at 10-17.4 GHz. The analysis of the broadband spectra recorded in this work was carried out with the newly developed AABS software package for Assignment and Analysis of Broadband Spectra, and precise spectroscopic constants are reported for the ground state, the first excited state of the low-frequency skeletal torsional mode ν₂₄, and the first excited state of the methyl torsional mode ν₂₃. Limited results have also been obtained for several higher excited states. The dataset for the ground state currently exceeds 1500 lines and for both the A and E internal rotor sublevels spans the complete range of values of K_a at the mid values of J for the measured transitions. The results were analysed with three freely available computer programs employing different strategies for dealing with internal rotation and a comparative discussion of their merits is made.     

Electric dipole moments of acrylonitrile and of propionitrile measured in supersonic expansion

New determinations of the ground-state electric dipole moments of acrylonitrile and propionitrile have been made from Stark effect measurements at conditions of supersonic expansion. The measurements were made on selected Stark lobes of fully resolved hyperfine components of several lowest-J rotational transitions. The results are μ_a = 3.821(3) D, μ_b = 0.687(8) D, μ_tot = 3.882(3) D for acrylonitrile, and μ_a = 3.816(3) D, μ_b = 1.235(1) D, μ_tot = 4.011(3) D for propionitrile. The new value of μ_b for acrylonitrile is appreciably different from those reported previously and it has been substantiated by both ab initio calculations and relative intensity measurements. The new dipole moment implies a considerable revision in the calculated intensities of the strongest THz-region rotational transitions of acrylonitrile, to 59% of previous values.     

High resolution scanning tunneling spectroscopy of ultrathin Pb on Si(1 1 1)-(6 × 6) substrate

The electronic structure of Si(1 1 1)-(6 × 6)Au surface covered with submonolayer amount of Pb is investigated using scanning tunneling spectroscopy. Already in small islands of Pb with thickness of 1 ML Pb_(1 1 1) and with the diameter of only about 2 nm we detected the quantized electronic state with energy 0.55 eV below the Fermi level. Similarly, the I(V) characteristics made for the Si(1 1 1)-(6 × 6)Au surface reveal a localized energy state 0.3 eV below the Fermi level. These energies result from fitting of the theoretical curves to the experimental data. The calculations are based on tight binding Hubbard model. The theoretical calculations clearly show prominent modification of the I(V) curve due to variation of electronic and topographic properties of the STM tip apex.