An unsymmetrical behavior of reactant units in the Kolbe�CSchmitt reaction

Paths of the Kolbe?CSchmitt reaction were investigated by the use of RB3LYP/6-311(+)G(d,p) density functional theory calculations. In a monomer model composed of C₆H₅O^?, Na⁺ and CO₂ affording sodium salicylate [C₆H₄(OH)CO₂ ^?Na⁺], a proton-shift step (Z Naturforsch 57a:812, 2002) was found to have an unrealistically large activation energy. In consideration of the phenol volatilization in the Kolbe??s experiment and the need of the linearity of the proton-transfer path, a dimer model was constructed. Again, a mutual proton-transfer step has a large activation energy. Alternatively, in a dimer model, a transfer path where the phenoxide ion in one monomer acts as a proton acceptor was found to have a reasonable energy. Addition of one more sodium ion leads to the significant lowering of activation energies. Thus, in the dimer, two monomers behave differently (A?+?A????A?+?B); one is as if it were a catalyst.     

Determining Stress–Strain in Rubber with In-Plane Biaxial Tensile Tester

The nominal stress–strain relationships of industrial rubber materials under multiaxial deformation are essential for precisely determining the constitutive laws of those materials. This paper proposes a new method for precisely estimating the nominal stress–stretch relationships of carbon-black-filled styrene butadiene rubbers (SBRs) under uniaxial tension, pure shear, and equibiaxial tension by using an in-plane biaxial tensile tester. The proposed method employs sheet-shaped rubber samples with notches for the pure-shear and equibiaxial tension tests to mitigate the influence of non-uniform deformation around the clamps. Finite element analysis and biaxial tensile tests were performed to verify the effectiveness of the proposed method. Performance evaluations based on both numerical calculations and experiments revealed that the proposed method enabled the precise calculation of the nominal stress–stretch relationship for uniform deformation from a tensile load and deformation of the reference area defined at the center of the samples.     

Electron-phonon interactions in charged cubic fluorocarbon cluster, (CF)8

Electron-phonon interactions in the charged cubic fluorocarbon, (CF)8 are studied, and compared with those in charged (CH)8 and (CD)8. The A1g mode of 1470 cm(-1) much more strongly couples to the a1g lowest unoccupied molecular orbitals (LUMO) than the A1g mode of 554 cm(-1) in (CF)8. The T2g mode of 1030 cm(-1), the Eg mode of 980 cm(-1), and the A1g mode of 1470 cm(-1) strongly couple to the t2u highest occupied molecular orbitals (HOMO) in (CF)8. The total electron-phonon coupling constants for the monoanion (l(-1)) and monocation (l(+1)) of (CF)8 are estimated to be 0.932 and 0.585 eV, respectively. The logarithmically averaged phonon frequencies for the monoanion (omega(ln,-1)) and monocation (omega(ln,+1)) of (CF)8 are estimated to be 1365 and 998 cm(-1), respectively. The l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution in cubane. The larger displacements of carbon atoms in the high frequency vibronic active mode in (CF)8 than those in (CD)8 due to larger atomic mass of fluorine than that of deuterium, and the unchanged electron distributions in the LUMO somewhat localized on carbon atoms as a consequence of H-F and H-D substitution in cubane, are the main reason why the l(-1) and omega(ln,-1) values increase much more significantly by H-F substitution than by H-D substitution. The l(+1) and omega(ln,+1) values less significantly change than the l(-1) and omega(ln,-1) values by H-F substitution as well as by H-D substitution in cubane. This is because the t2u HOMO in (CF)8 and the t2g HOMO in (CH)8 are somewhat localized on fluorine atoms, and thus, the high frequency vibronic active modes in which the displacements of carbon atoms are large cannot necessarily very strongly couple to the HOMO somewhat localized on fluorine atoms in (CF)8.     

On the Hartree-Fock approximation to the electronic structure of molecule in the intense radiation field and the strong vibronic coupling

The Hartree-Fock approximation has been generalized to incorporate the nonadiabatic effect of molecular vibration previously by Tachibana et al. Here, we will derive the Hartree-Fock equation which reflects also the nonlinear effect of the infrared radiation field as well by using the Bloch-Nordsieck transformation which was discussed first by Nguyen-Dang and Bandrauk in the field of molecular physics. The Hartree-Fock equation reflects the non-adiabatic coupling between an electron and a molecular vibration and between the electron and a infrared radiation fields. The infrared radiation field also affects the dynamics of nuclear motion.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday     

ESR studies of polyacenic semiconductive material

ESR measurements have been performed on the polyacenic material prepared by the pyrolytic treatment of phenol-formaldehyde resin. Six kinds of samples (A)-(F) with various electrical conductivity (σ) were employed for the measurements. Each sample shows a single narrow line, the g-values of which suggest the existence of unpaired electrons of π-type. If the sample (F) (σ = 1 × 10° S cm^?1) the single narrow line becomes drastically diminished in the presence of a small amount of oxygen.     

A hydrogen rearrangement of formamidine and the solvent effects thereupon

The nature of the 1,3 hydrogen rearrangement of formamidine (H₂N-CH=NH) and the solvent effects on that reaction are studied with ab initio molecular orbital calculations on the basis of the supermolecule model. The reaction path and the motion of the migrating hydrogen atom are traced by using the concept of the intrinsic reaction coordinate (IRC). Four types of orientation of one water molecule to formamidine at the transition state of reaction are examined and the results are discussed from the standpoint of the orbital interactions.