Protonation susceptibility of functional groups: A new parameter for interpreting chemical ionization mass spectra of bifunctional organic compounds

A new parameter, the protonation susceptibility (PS), of functional groups in the chemical ionization mass spectrometry of bifunctional organic compounds is presented. In terms of quasi-equilibrium theory of unimolecular decomposition of the molecular protonated ion of [MH]⁺, the relative PS corresponds to the relative area under P(E) curves of [MH]⁺ ions that have a proton at different functional groups. Numerical evaluation of the PS values of pertinent functional groups was made by using particularly selected compounds. The results clearly indicate that PS is independent of proton affinity (PA).     

Spectroscopic and theoretical studies of optically active porphyrin dimers: a system uninterpretable by exciton coupling theory.

The electronic excited states of a meso-meso beta-beta doubly linked bis-porphyrin are comprehensively investigated by measuring its circular dichroism (CD) and magnetic circular dichroism (MCD) spectra. The observed spectroscopic properties are rationalized by DFT calculations. The frontier molecular orbitals (MOs) are constructed by the linear combinations of the constituent monomers' four MOs. Comparison of a theoretical CD spectrum based on time-dependent DFT (TDDFT) with the experimental spectra resulted in the assignment of the helical conformation of the dimer. This assignment is contrary to the previous assignment based on the point-dipole approximation (exciton coupling theory).     

Raman and infrared spectra of the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers of β-carotene: Key bands distinguishing stretched or terminal-bent configurations form central-bent configurations

Raman and infrared spectra in the region of 1800-150 cm⁻¹ were recorded for a set of cis-trans isomers of d̃-carotene, i.e. the all-trans, 7-cis, 9-cis, 13-cis and 15-cis isomers. Spectral comparison revealed Raman and infrared key bands which (1) distinguish stretched or terminal-bent configurations (all-trans, 7-cis and 9-cis) from central-bent configurations (13-cis and 15-cis), and (2) distinguish unmethylated 7-cis and 15-cis configuratios. Keybands (1) include Raman bands at 1160 and 1140 cm⁻¹ and infrared bands at 825 and 775 cm⁻¹ (the intensity varies with the position of the cis-bend) Key bands (2) include Raman bands at 1274 and 962 cm⁻¹ and an infrared band at 741 cm⁻¹ (characteristic of the 7-cis configuration), and also a Raman band at 1247 cm⁻¹ and an infrared band at 775 cm⁻¹ (characteristic of the 15-cis configuration). The normal modes for the key bands were determined by a set of normal coordinate calculations for the isomeric configurations of a simplified model of d̃-carotene. The key bands were mainly related to the C H in-plane bendings, coupled with the CC or C C stretching, or to the C H out-of-plane wagging vibrations, some of which coupled with the CC torsion.     

Corrigendum to “Constraints on operator ordering from third quantization” [Ann. Phys. 365 (2016) 54–65]

In our previous paper Ohkuwa et al. (2016) corrigendum was found in Eqs. (3.4) and (3.6). However, conclusions of our previous paper are not changed.     

Nano-structured surfaces on Ni–Ti generated by multiple shots of interfering femtosecond laser

Combined periodic structures composed of micron-sized periodic structure and nano-sized quasi periodic structure were generated on Ni–Ti target by multiple shots of interfering femtosecond laser beams. The micron-sized structure was generated by the interference pattern of four beams, and the nano-sized quasi period was generated due to the multiple shot effect of femtosecond laser. The structures were investigated in detail by two-dimensional fast Fourier transform (2D-FFT). The power spectra showed small spots and fuzzy spots due to precise period and quasi period, respectively. The most major size of the quasi periodic structure was 580 nm.     

Photocurrent generation system incorporated with antenna function

Porphyrin accumulation onto a self-assembled monolayer (SAM) of imidazole-substituted porphyrins by a supramolecular method to form a chain structure leads to significant increase of light absorption in the visible light region and therefore photocurrents.     

Hyperfine structure of the electron spin resonance of phosphorus-doped Si nanocrystals

Electronic states of P donors in Si nanocrystals (nc-Si) embedded in insulating glass matrices have been studied by electron spin resonance. Doping of P donors into nc-Si was demonstrated by the observation of optical absorption in the infrared region due to intraconduction band transitions. P hyperfine structure (hfs) was successfully observed at low temperatures. The observed splitting of the hfs was found to be much larger than that of the bulk Si:P and depended strongly on the size of nc-Si. The observed strong size dependence indicates that the enhancement of the hyperfine splitting is caused by the quantum confinement of P donors in nc-Si.