Analysis of some combination-overtone infrared bands of SO3

Several new infrared absorption bands for ³²S¹⁶O₃ have been measured and analyzed. The principal bands observed were ν₁+ν₂ (at 1561 cm⁻¹), ν₁+ν₄ (at 1594 cm⁻¹), ν₃+ν₄ (at 1918 cm⁻¹), and 3ν₃ (at 4136 cm⁻¹). Except for 3ν₃, these bands are very complicated because of (a) the Coriolis coupling between ν₂ and ν₄, (b) the Fermi resonance between ν₁ and 2ν₄, (c) the Fermi resonance between ν₁ and 2ν₂, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A₁^′ and A₂^′ levels of ν₃+ν₄. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν₃ band was an essential aid in fitting the ν₃+ν₄ transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A₁^′ vibrational level is 3.50 cm⁻¹ above the A₂^′ level, i.e., r₃₄=1.75236(7) cm⁻¹. In the case of the 3ν₃ band, the spectral analysis is straightforward and a weak Δk=±2, Δl₃=±2 interaction between the l₃=1 and l₃=3 substates locates the latter A₁^′ and A₂^′ “ghost” states 22.55(4) cm⁻¹ higher than the infrared accessible l₃=1 E^′ state.     

Stable Subnorms II

In this paper we continue our study of stability properties of subnorms on subsets of finite-dimensional, power-associative algebras over the real or the complex numbers.     

Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Role of water vapor and CO2 in the paleoclimatic fluctuations along northwestern and southern Syria, and the adjacent Mediterranean Sea

Microscopic petrified grains were collected from a mafic–ultramafic pipe, NE of Dreikeesh, NW Syria. The grains were identified as anthers/gynoecia in herb/grass flowers. Three of the grains showed evidence of magnetism, two slowly dissolved in concentrated HCl, and three microprobed grains showed a montmorillonitic composition. Iron originating from pyroxene was oxidized to magnetite. Released silica formed the mineral suite agate–chalcedony–opal. Warm/cold paleoclimatic fluctuations, occurring during late Pliocene–Holocene, depended on water vapor, CO₂ production, and cinders in the atmosphere. Most of these were associated with changing volcanic/tectonic events. Fluctuations were controlled by heat reflected from the Earth's surface being absorbed by water vapor and CO₂, which both re-reflected the heat back to the surface, thus, raising the temperature. This cycle was repeated several times during late Pliocene–Holocene.     

Probing the surface structure of quasicrystals via angle-resolved low-energy ion scattering

Angle-resolved low-energy ion scattering is a valuable technique for examining the topmost surface layers of materials. Using this technique, information about both composition and structure can be obtained. We discuss the physical basis of this technique and present our findings for the fivefold surface of icosahedral (i-) Al–Pd–Mn. Our results clearly show that the exposed surface has a higher Al content than the bulk and can have fivefold periodicity. Information about frequently occurring interatomic distances on the surface can also be obtained by this technique. We discuss the results and compare them to recent scanning tunneling microscopy studies and to bulk structure models.     

Structure–electrical property study of anisotropic polyaniline films

The relationships of the structure and electrical properties of anisotropic HCl‐doped polyaniline (PANI) films cast from N,N′‐dimethylpropylene urea (DMPU) solutions and stretched to different draw ratios were studied. The anisotropic structure of the stretched PANI films was examined by X‐ray diffraction, near‐infrared wave‐guide coupling, and polarized infrared measurements. The PANI emeraldine base (EB) films cast from DMPU solutions had a single‐phase noncrystalline structure, and stretching of the films did not cause crystallization to occur. The transition moment angles of two weakly absorbing infrared bands were determined, and the Hermans' orientation functions for the PANI EB films were calculated. The PANI films were then doped with HCl, and the electrical properties were determined by impedance spectroscopy. With a specially designed test fixture, the in‐plane and through‐plane impedance was obtained. The conductivity along the stretch direction increased with orientation. The in‐plane conductivity was significantly higher than the through‐plane conductivity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 823–841, 2003     

Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007