Interrelationship between superprotonic conductivity and strain in CsHXO4

In order to clarify the mechanism of superprotonic conductivity (SPC) for the hydrogen-bonded compound CsHXO₄ (X=S, Se), we have investigated the elastic properties of CsHXO₄ with various transition temperatures (T_c), at which CsHXO₄ exhibits a structural phase transition from a low-temperature monoclinic phase with low protonic conductivity (phase II) to a high-temperature SPC phase (phase I). It was found that, in CsHS_xSe_1 − xO₄ (x=0–1), the transition temperature T_c decreases in proportion to the square of spontaneous strain b in the a_II–b_II plane of phase II. This result indicates that the spontaneous strain in the a_II–b_II plane plays an important role in the appearance of SPC in CsHXO₄. Moreover, thermodynamic analyses suggest that proton migration in phase I is induced by the release of the strain energy. From these results, it is deduced that the phase transition temperature in CsHXO₄ is determined by the competition between the kinetic energy of proton and the released-strain energy.     

Comparative Investigation on the Concentration-Dependences of the Half-Band Widths of Infrared Absorption and Raman Bands

It is demonstrated that the fashions of the concentration-dependences of half-band widths are markedly different between the corresponding bands in i.r. absorption and Raman spectra when the i.r. absorption intensities of the bands are extremely large. On the other hand, when the i.r. intensities are not so great, the similar behaviour is observed for the changes in the half-band widths. In this study, these phenomena have been discussed in terms of the vibrational relaxation of resonance type and the local field effect.     

Synthesis and properties of 2-azidodeoxyadenosine and its incorporation into oligodeoxynucleotides

2-Azidodeoxyadenosine (7) was conveniently synthesized from deoxyguanosine (2) by use of a combined reagent of TMSN₃–BuONO. The structure of the tautomer of the azido derivative was determined by ¹H NMR. Reaction of 7 with iPr₂NP(OEt)₂ gave an intermediate 10 of the Staudinger reaction. Incorporation of 7 into a DNA 13mer resulted in a significant decrease of the T_m value of the DNA duplex upon hybridization with the complementary strand. The thermal stability was discussed based on the hydrogen bond energy and electrostatic repulsion.     

The Sensitization Effect in the Laser-Induced Infrared Fluorescence Spectroscopy by Addition of SF6. II

The sensitization effect in the IR-F spectroscopy by addition of SF₆ was investigated in case of acetone as a sample. We kept the partial pressure of acetone constant, varied that of SF₆, and investigated the variations of the degree of sensitization. The experimental data shows that the degree of sensitization increases steeply and is saturated as the partial pressure of SF₆ becomes higher. The results were examined in terms of the kinetics of the intra-and intermolecular energy transfer involved in the emission of infrared radiation in question.     

The use of sulfur ylides in the synthesis of 3-alkyl(aryl)thio-4-trifluoromethylpyrroles from mesoionic 4-trifluoroacetyl-1,3-oxazolium-5-olates

In this report, we describe a new method for the synthesis of densely functionalized pyrroles. Reaction of mesoionic 1,3-oxazolium-5-olates with various S-ylides proceeds via nucleophilic addition followed by opening of the oxazole ring and subsequent cyclization to multisubstituted pyrroles bearing both a trifluoromethyl and alkyl(aryl)thio group at 3- and 4-positions.     

Explicitly correlated wave functions: summary and perspective

We summarize explicitly correlated electronic structure theory in perspective of future work in the field. Earlier stages of approaches with different Ansätze in physics and chemistry are described. We then discuss recent advances focusing on explicitly correlated wave functions using cusp conditions. Removal of Coulomb singularities in terms of the rational generator is brought out from the viewpoint of many-body perturbation theory. On the basis of decomposition schemes for many-electron integrals in R12 and F12 methods, we further discuss the possibility of increasing the accuracy of molecular numerical integration and massively parallel calculations of explicitly correlated methods.     

NMR and magnetic studies on 7 K anomaly in Tl3H(SO4)2

Measurements of the spin-lattice relaxation time, NMR absorption line and magnetization have been carried out on the Tl₃H(SO₄)₂ crystal below 50 K. The anomaly at around 7 K was: (1) the spin-lattice relaxation times of ¹H and ²⁰⁵Tl nuclei increase steeply with decreasing temperature below 7 K, (2) the NMR absorption lines below 7 K shift to the high-magnetic field side in comparison with that above 7 K, and (3) the ¹H NMR line width exhibits a drastic increase of the line width with decreasing temperature below 7 K. These results indicate that the magnetic dipole fluctuation of the proton changes at 7 K. On the other hand, there are no remarkable anomalies of magnetic susceptibility at around 7 K. From these results it is deduced that the anomaly at around 7 K is caused by the change in quantum mechanical process of the proton from proton tunneling to zero-point vibration of hydrogen in the hydrogen bond with the decrease of temperature.     

Hyperfine Fields of Sr and Y in Ferromagnetic Hosts, and Magnetic Moment of 93Y

Recent studies of hyperfine fields B _HF of Sr and Y in Fe are briefly reviewed. The B _HF value of Y in Ni is given by NMRON of ^91mYNi. The nuclear magnetic moment of the ground state of ⁹³Y is extracted from the β-ray detected NMRON of ⁹³YFe.