3s Rydberg and cationic States of pyrazine studied by photoelectron spectroscopy

We have studied 3s(n-1 and pi-1) Rydberg states and D0(n-1) and D1(pi-1) cationic states of pyrazine [1,4-diazabenzene] by picosecond (2 + 1) resonance-enhanced multiphoton ionization (REMPI), (2 + 1) REMPI photoelectron imaging, He(I) ultraviolet photoelectron spectroscopy (UPS), and vacuum ultraviolet pulsed field ionization photoelectron spectroscopy (VUV-PFI-PE). The new He(I) photoelectron spectrum of pyrazine in a supersonic jet revealed a considerably finer vibrational structure than a previous photoelectron spectrum of pyrazine vapor. We performed Franck-Condon analysis on the observed photoelectron and REMPI spectra in combination with ab initio density functional theory and molecular orbital calculations to determine the equilibrium geometries in the D0 and 3s(n-1) states. The equilibrium geometries were found to differ slightly between the D0 and 3s states, indicating the influence of a Rydberg electron on the molecular structure. The locations of the D1-D0 and 3s(pi-1)-3s(n-1) conical intersections were estimated. From the line width in the D1 <-- S0 spectrum, we estimated the lifetime of D1 to be 12 fs for pyrazine and 15 fs for fully deuterated pyrazine. A similar lifetime was estimated for the 3s(pi-1) state of pyrazine by REMPI spectroscopy. The vibrational feature of D1 observed in the VUV-PFI-PE measurement differed dramatically from that in the UPS spectrum, which suggests that the high-n Rydberg (ZEKE) states converging to the D1 vibronic state are short-lived due to electronic autoionization to the D0 continuum.     

Fluorescence and electrochemical detection of pyrimidine/purine transversion by a ferrocenyl aminonaphthyridine derivative

A novel hydrogen bond-forming ligand for pyrimidine/purine transversion, which contains both a fluorescent naphthyridine moiety and a ferrocenyl group as an electrochemical indicator, is described. Hydrogen bond-mediated recognition for a target nucleobase at an abasic site in a DNA duplex is confirmed by both fluorescence and electrochemical measurements. The analysis by fluorescence titration reveals that the ligand shows significant fluorescent quenching upon formation of a 1 : 1 complex with the target nucleobase opposite the abasic site, and the selectivity is in the order of cytosine > thymine > adenine, guanine, reflecting the stability of the hydrogen bond formation.     

Resonant speed meter for gravitational-wave detection

Gravitational-wave detectors have been well developed and operated with a high sensitivity. However, they still suffer from mirror displacement noise. In this Letter, we propose a resonant speed meter as a displacement noise-canceled configuration based on a ring-shaped synchronous recycling interferometer. The remarkable feature of this interferometer is that, at certain frequencies, gravitational-wave signals are amplified, while displacement noises are not.     

New magnetic field effects observed in micellar and fluid solutions under ultrahigh fields of up to 30 T

With magnetic fields of up to 30 T, we have found the saturation and reversion of magnetic field effects (MFEs) on radical pair lifetimes and escape radical yields due to the relaxation mechanism for the photoreduction of carbonyl compounds in micellar solutions as well as the saturation of MFEs on the escape radical yield due to the Δg mechanism for the photoreduction of 4-methoxy-benzophenone with thiophenol in fluid solutions. We have also found large MFEs for several reactions involving three odd electrons in fluid solutions.     

High-Speed voltammetry of Mn-doped LiCoO2 using a microelectrode technique

The microelectrode technique was applied to investigate the electrochemical properties of LiCo_{1- x} Mn _x O₂ (x=0, 0.01, 0.05, 0.2, or 0.5) synthesized using the citrate process. From the X-ray diffraction measurements, an expansion of the c-axis and a decrease in the crystal size of the materials were observed on substitution of Mn into LiCoO₂. In the electrochemical measurements, the high-speed cyclic voltammogram for the Mn-substituted materials gave one set of peaks at 3.9 V vs. Li/Li⁺. The apparent chemical diffusion constant (D _app) of LiCo_0.8Mn_0.2O₂ obtained from the potential step experiment was 6.4 × 10⁻⁸ cm²/s, which is larger than that of LiCoO₂. The increase in D _app is attributable to the expansion of the c-axis and/or the decrease in the crystal size. In addition, the increase in Mn substitution up to 20% lead to an improvement in the kinetic reversibility and the cycle stability of LiCoO₂. Received: 7 June 1999 / Accepted: 25 June 1999     

Lewis Acid-Mediated Decarboxylative Allylation of Enol Carbonates

A homoallylic ketone can be transformed and functionalized by various synthetic reactions, and thus, is regarded as one of the representative building blocks in organic chemistry. An additional route to access homoallylic ketones, namely, a Lewis acid-mediated decarboxylative allylation of cyclic enol carbonates, prepared by fixation of carbon dioxide onto propargyl alcohols, was developed in this work. The treatment of a cyclic enol carbonate with a Lewis acid in the presence of an allylsilane resulted in the formation of a homoallylic ketone. It was found that the title reaction proceeded well by the combined use of zirconium tetrachloride with allyltrimethylsilane. The allylation occurred with high regioselectivity and the corresponding homoallylic ketones were obtained in good-to-high yields. A reaction mechanism involving the decarboxylative formation of an oxyallyl cation equivalent is proposed.     

Observing the Stimulated Raman Gain Spectra of Solutions Using an Infrared Pump Pulse with Narrow Linewidth and a Low-Noise CW Probe Laser

Stimulated Raman gain (SRG) spectroscopy using infrared pump pulses with narrow linewidth and a low-noise cw probe infrared laser was proposed. High-resolution Raman spectra of solutions were obtained. The SRG spectra of crystal GaP, benzene, and toluene were measured to confirm the spectral resolution and sensitivity over the terahertz (THz) region. We discuss the polarization dependence of the spectral measurement of carbon tetrachloride. Our system can detect organic molecules in aqueous solutions.     

NOVEL TERAHERTZ PHOTOCONDUCTIVE ANTENNAS

The photoconductive (PC) antenna is a key device for the recent terahertz (THz) photonics based on laser-pumped generation and detection of THz radiation. In this paper we report on two new types of PC antennas: the Schottky PC antenna and the multi-contacts PC antenna. The former one is able to detect THz radiation intensity without the time-delay scan and useful for applications where spectroscopic information is not important, such as the THz intensity imaging. The latter one is useful for the polarization sensitive THz spectroscopy, such as the THz ellipsometry. The characteristic features of these new types of PC antennas are studied by using a THz time-domain spectroscopy system.     

Quantum chemistry beyond Born–Oppenheimer approximation on a quantum computer: A simulated phase estimation study

We present an efficient quantum algorithm for beyond‐Born–Oppenheimer molecular energy computations. Our approach combines the quantum full configuration interaction method with the nuclear orbital plus molecular orbital method. We give the details of the algorithm and demonstrate its performance by classical simulations. Two isotopomers of the hydrogen molecule (H₂, HT) were chosen as representative examples and calculations of the lowest rotationless vibrational transition energies were simulated. © 2016 Wiley Periodicals, Inc.