Electronic structure and the hydrogen-shift isomerization of hydrogen nitryl HNO2

Summary Electronic structure of hydrogen nitryl HNO₂, a yet not identified entity, and the path of its possible isomerization totrans-HONO have been investigated byab initio SCF and MRD-CI computations using the 6-31G** basis set. HNO₂ isC _2v -symmetric and its ground state (¹ A ₁) is less stable thantrans-HONO by 66 kJ/mol (with the SCF vibrational zero-point energy correction). The lowest two excited singlet states (¹ A ₂ and¹ B ₁) are nearly degenerate, their vertical excitation energies being predicted to be 4.8 eV. The isomerization path is traced by the CASSCF procedure and the activation barrier height is evaluated by the CI treatment. HNO₂ in its ground state isomerizes totrans-HONO by maintaining the planar (C _s-symmetric) structure. The activation energy is calculated to be 171 kJ/mol, which is clearly lower than the calculated H-N bond energy (253 kJ/mol). The transition state seems to be more adequately described as an interacting system of proton and the nitrite anion rather than as a pair of two fragment radicals.     

Preparation of halo-F-methanes via potassium fluoride-halogen cleavage of halo-F-methylphosphonium salts

Treatment of halo-$\text{F}$-methylphosphonium salts with potassium fluoride and halogen (I₂, Br₂, ICl, IBr) gives modest yields of halo-$\text{F}$-methanes. This method of preparation augments the classical Hunsdiecker approach to these materials.     

Upward temperature shift of the intrinsic phase lag of the magnetization of Bis(phthalocyaninato)terbium by ligand oxidation creating an S = 1/2 spin

An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons.     

Synthesis and structure of 16 pi octaalkyltetraphenylporphyrins

The oxidized octaethyltetraphenylporphyrin (1, OETPP) and the corresponding newly prepared octaisobutyltetraphenylporphyrin (3, OisoBuTPP) could be isolated from the reaction of OETPPLi2 (or OisoBuTPPLi2) with SOCl2. The X-ray analysis and the characteristic UV-vis spectra of 1 and 3 revealed that these are the first examples of 16 pi nonaromatic porphyrins.     

Mevashuntin, a novel metabolite produced by inhibition of the mevalonate pathway in Streptomyces prunicolor

Inhibition of the mevalonate pathway by an HMG-CoA reductase inhibitor, mevalotin, in Streptomyces prunicolor possessing both mevalonate and MEP pathways resulted in the production of a new metabolite mevashuntin that consisted of conjugated thiazolone and pyranonaphthoquinone moieties.     

Existence Theorems for Set-valued Operators in Banach Spaces

In this paper, we study the problem of existence of zero points for set-valued operators in Banach spaces. We present a simple condition which can be used to verify that under some conditions, set-valued operators have zero points. Furthermore, we derive the surjectivity result and the Kakutani fixed point theorem by using this condition.      

Optical and Thermal Simulator for Laser-assisted Magnetic Recording

“Laser-assisted magnetic recording”, in which a recording media is heated by a laser beam while writing data, is attracting attention as a technology that enables a recording density of 1 Tb/in.². There exists another technology for media in which the recording layer is constructed with many small projections that enable high magnetic coercivity. This is called “patterned media”. For developing hard disk drives using these methods, we developed a simulator that analyzes the optical intensity distribution from the optical head for laser-assisted recording and the temperature profile on the patterned media. The simulator calculates the optical model using the finite-difference time-domain (FDTD) method. The thermal analysis of the three-dimensional model allows fast calculations using the alternating direction implicit (ADI) method. The heat source distribution data for thermal analysis is calculated in order to use the results of optical analysis. The optical and thermal analyses of the laser-assisted recording model were investigated with the simulator.     

Remarkable Suppression of [2+2] Cycloaddition during Nonresonant Two-photon Photoreaction of trans-Stilbene in the Presence of Tetramethylethylene

Abstract— Nonresonant two-photon excitation of /rans-stilbene in the presence of an excess amount of tetramethylethylene induced predominantly cis-trans isomerization; the [2+2] intermolecular cycloaddition pathway was remarkably suppressed, in contrast to the one-photon excitation under similar conditions, where the cycloaddition is known to be the major pathway.