Mechanism of poly(N-isopropylacrylamide) cononsolvency in aqueous methanol solutions explored via oxygen K-edge X-ray absorption spectroscopy.

The cononsolvency mechanism of poly(N-isopropylacrylamide) (PNIPAM), dissolving in pure methanol (MeOH) and water (H2O) but being insoluble in MeOH-H2O mixtures, was investigated by O K-edge X-ray absorption spectroscopy (XAS). The cononsolvency emerges from the aggregation of PNIPAM with MeOH clusters, leading to the collapse of the hydrophobic hydration of PNIPAM.

Experimental and Theoretical Study for Core Excitation of Firefly Luciferin in Carbon K-Edge Spectra.

Carbon (C) K-edge X-ray absorption spectra for firefly luciferin were measured and assigned using time-dependent density functional theoretical calculations for luciferin anion and dianion to elucidate the effect of hydroxy-group deprotonation. It was found that the C K-edge spectra for luciferin had four characteristic peaks. The effect of deprotonation of the hydroxy group appears in the energy difference of the first and second peaks of these spectra. This energy difference is 1.0 eV at pH 7 and 2.3 eV at pH 10. The deprotonation of the hydroxy group can be distinguished based on the soft X-ray absorption spectra.

Operando time-resolved soft x-ray absorption spectroscopy for photoexcitation processes of metal complexes in solutions.

Operando time-resolved soft x-ray absorption spectroscopy (TR-SXAS) is an effective method to reveal the photochemical processes of metal complexes in solutions. In this study, we have developed the TR-SXAS measurement system for observing various photochemical reactions in solutions by the combination of laser pump pulses with soft x-ray probe pulses from the synchrotron radiation. For the evaluation of the developed TR-SXAS system, we have measured nitrogen K-edge x-ray absorption spectroscopy (XAS) spectra of aqueous iron phenanthroline solutions during a photoinduced spin transition process. The decay process of the high spin state to the low spin state in the iron complex has been obtained from the ligand side by N K-edge XAS, and the time constant is close to that obtained from the central metal side by time-resolved Fe K-edge XAS in the previous studies.

Generation of sub-half-cycle 10 µm pulses through filamentation at kilohertz repetition rates.

We have experimentally demonstrated the generation of sub-half-cycle phase-stable pulses with the carrier wavelength of 10.2 µm through two-color filamentation in nitrogen. The carrier-envelope phase (CEP) of the MIR pulse is passively stabilized and controlled by the attosecond time delay between the two-color input pulses. The duration of the MIR pulse is 13.7 fs, which corresponds to 0.402 cycles. The absolute value of the CEP of the generated sub-half-cycle pulse is consistent with a simple four-wave difference frequency generation model. We have also found that the 10 kHz repetition rate of the light source causes the fluctuation of the pulse energy on a few hundred millisecond time scale.

High-harmonic generation in solids driven by subcycle midinfrared pulses from two-color filamentation.

Carrier-envelope-phase (CEP) controlled subcycle midinfrared pulses generated through two-color filamentation have been applied for high-harmonic (HH) generation in a crystalline silicon (Si) membrane. The HH spectrum reaches the ultraviolet region (<300 nm), beyond the direct band gap of Si. The shape of the HH spectrum strongly depends on the CEP. The complex CEP dependence can be explained with the interference between different orders of the harmonics. The complete waveform characterization of the subcycle driver pulse using frequency-resolved optical gating capable of CEP determination plays a crucial role for investigation of the subcycle dynamics.