Vibrational analysis and conformational studies of allylamine

Infrared absorption spectra of allylamine and its amino-deuterated species were observed in the gas phase and in the low-temperature Ar matrix. An analysis of the spectra showed that there exist mainly three rotational conformers, and possibly one other conformer as a minor component. At room temperature, the skew forms around the CC bond populate about 70%, while the rest are assigned to the cis form(s). On the other hand, two forms around the CN bond, gauche and trans, exist with about equal populations.     

α + 14C molecular states in 18O

The possible existence of α + ¹⁴C molecular states in ¹⁸O is investigated in a coupled-channel orthogonality-condition model. Comparison with experiment, specifically E1, E2 transition probabilities and reduced α-widths, shows that the assumption of a single molecular configuration for the so-called dipole band is inappropriate. The result of calculation further makes it possible to single out a few molecular bands in ¹⁸O.     

237Np and 57Fe Mössbauer study of NpFeGa5

⁵⁷Fe and ²³⁷Np Mössbauer ōmeasurements have been performed for NpFeGa₅, which is one of the so-called neptunium 1-1-5 compounds. The ⁵⁷Fe Mössbauer spectra below T _N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the ⁵⁷Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the ²³⁷Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the ²³⁷Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μ_B using the Np atomic magnetic moment of 0.86 μ_B determined by the neutron diffraction study.     

Second Harmonic Generation Measurements for Biomacromolecules: Celluloses

The molecular chain orientation of mercerized cellulose II was examined by optical second harmonic generation (SHG) measurements. The SHG intensities of several kinds of mercerized cellulose II were found to be much larger than those expected for a structural model with an antiparallel molecular chain orientation as proposed by X-ray studies. This result suggests that the orientation of mercerized cellulose II is parallel as suggested by molecular dynamics simulation. © 2004 The Optical Society of Japan     

Ultraviolet photoemission spectroscopy of (TaSe4)2I

The vacuum ultraviolet photoemission spectra of quasi-one-dimensional charge density wave ( CDW ) system, (TaSe₄)₂I, were measured for photon energies between 32 and 100 eV at room temperature ( in the normal phase ) and at about 100 K ( in the CDW phase ). The spectrum of Ta 4f core-levels has shown no additional splitting due to the two different Ta sites. The spectra of the valence and conduction bands have revealed the resonant enhancement for the excitation of the Ta 5p core states, which demonstrates the remarkable hybridization of Ta 5d orbitals with Se 4p orbitals with binding energies smaller than 4 eV. In the CDW phase, the partial cross section decreases for both Ta 5d bands and Se 4p bands with Ta 5d components.     

Theoretical study of resonant-tunneling and confining phenomena with mass variation in unsymmetrical rectangular double-barrier structures

Analytical expressions for the transmission coefficient and the resonance condition in unsymmetrical rectangular double-barrier structures are derived theoretically by taking into account the mass difference between well and barrier layers. It is found that resonant tunneling with a transmission peak equal to 1 (unity resonance) and resonant tunneling with a transmission peak less than 1 (below unity resonance) may occur in the unsymmetrical double-barrier structures. Two independent conditions are required for unity-resonant transmission: One is the Phase-Difference Condition for Resonance (PDCR) and the other is the Maximum Condition for the Peak Value (MCPV). The below-unity resonant transmission occurs when only condition PDCR holds. It is believed that the two conditions are useful for calculating values of the transmission coefficient and the resonance energy for the unsymmetrical double-barrier structures. They may be useful for resonant tunneling-device fabrication. Furthermore, wave functions of an electron at resonance level are calculated and the confining phenomenon is confirmed.     

(Polyfluoro)silane-mediated generation of azomethine ylides from imines and their cycloaddition leading to N-heterocycles

The novel generation and cycloaddition of azomethine ylides from an α-(trimethylsilyl)imine using (polyfluoro)silanes is described. The method was successfully applied to an efficient one-pot process. Namely, an azaallyl anion, generated by abstraction of the hydrogen α to an imino nitrogen, was treated with a di- or trifluorosilane to give an azomethine ylide intermediate below room temperature. The generated 1,3-dipole was smoothly trapped with dipolarophiles to afford nitrogen-containing five-membered heterocycles in good yields.     

Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate anion

Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA^?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T₁) states ofp-MeCA andp-MeCA^?. From the analysis of these spectra we concluded that the deviation from planar structure in the T₁ state is small inp-MeCA andp-MeCA^? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T _y in bothp-MeCA andp-MeCA^?. However, following the deprotonation ofp-MeCA, (P _y?P _z)/(P _x?P _z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA^? (P _i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T₁ sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed.     

Generation and characterization of electrons from a gas target irradiated by high-peak-power lasers

We present the results of electron generation experiments conducted at the Advanced Photon Research Center, Japan Atomic Energy Research Institute, using 23-fs relativistically intense 20-TW tightly focused laser pulses with underdense plasma. We observed electron energies up to 40 MeV characterized by a two-temperature Maxwell distribution. With the help of particle-in-cell simulations, we found that these are due to different plasma wave-breaking processes. A charge of 5 nC/shot was obtained at a small solid angle, which corresponds to high peak current generation.