Investigation of the vibrational density of states of sodium carboxymethyl starch glass via terahertz time-domain spectroscopy.

We investigated the vibrational density of states of sodium carboxymethyl starch (CM-starch) by terahertz (THz) time-domain spectroscopy. The CM-starch showed a broad peak at ∼3 THz. The structure of the peak was similar to those corresponding to glucose-based polymer glasses possessing hydrogen bonds. The boson peak (BP) appeared at 1.16 THz at the lowest temperature and disappeared because of the existence of excess wing at higher temperatures. However, based on our novel BP frequency determination method using the inflection point of the extinction coefficient, the BP frequency showed almost no dependence on temperature. Further, the chain length dependence of the BP frequency of the glucose-based glasses showed that the BP frequency of the polymer glass was slightly lower than that of the monomer glass. The power law behaviour of the absorption coefficient suggested the existence of fractons, and the fractal dimension was estimated to be 2.33.

Examination of structure and optical properties of Ce3+-doped strontium borate glass by regression analysis.

Amorphous materials with non-periodic structures are commonly evaluated based on their chemical composition, which is not always the best parameter to evaluate physical properties, and an alternative parameter more suitable for performance evaluation must be considered. Herein, we quantified various structural and physical properties of Ce-doped strontium borate glasses and studied their correlations by principal component analysis. We found that the density-driven molar volume is suitable for the evaluation of structural data, while chemical composition is better for the evaluation of optical and luminescent data. Furthermore, the borate-rich glasses exhibited a stronger luminescence due to Ce3+, indicating a higher fraction of BO3/2 ring and larger cavity. Moreover, the internal quantum efficiency was found to originate from the local coordination states of the Ce3+ centres, independent of composition or molar volume. The comparison of numerical data of the matrix is useful not only for ensuring the homogenous doping of amorphous materials by activators, but also for determining the origin of physical properties.

Dynamical Collectivity and Nuclear Quantum Effects on the Intermolecular Stretching Mode of Liquid Water.

This study investigated the broadband terahertz and low-frequency Raman spectroscopy of liquid water (H2O, D2O, and H218O) over 2 decades of frequency to address long-standing challenges regarding the interpretation of the intermolecular stretching mode at around 5 THz. We experimentally demonstrated that the intermolecular stretching mode of liquid water obtained via terahertz spectroscopy is significantly redshifted and broadened compared with that via Raman. This result was rationalized by the enhanced dynamical collectivity probed by terahertz spectroscopy, although both have a common origin in the kinetic motion. Their temperature and isotope dependences emphasize the significance of oscillation mass in determining the intermolecular stretching lineshape, while quantum effects cannot be overlooked in both terahertz and low-frequency Raman spectra.

Detection of boson peak and fractal dynamics of disordered systems using terahertz spectroscopy.

The boson peak is a largely unexplained excitation found universally in the terahertz vibrational spectra of disordered systems; the so-called fracton is a vibrational excitation associated with the self-similar structure of monomers in polymeric glasses. We demonstrate that such excitations can be detected using terahertz spectroscopy. In the case of fractal structures, we determine the infrared light-vibration coupling coefficient for the fracton region and show that information concerning the fractal and fracton dimensions appears in the exponent of the absorption coefficient. Finally, using terahertz time-domain spectroscopy and low-frequency Raman scattering, we experimentally observe these universal excitations in a protein (lysozyme) system that has an intrinsically disordered and fractal structure and argue that the system should be considered a single supramolecule. These findings are applicable to amorphous and fractal objects in general and will be valuable for understanding universal dynamics of disordered systems via terahertz light.

Photocatalytic hydrogen generation of monolithic porous titanium oxide-based glass-ceramics.

A large relative surface area is crucial for high catalytic activity. Monolithic catalysts are important catalytic materials because of minimal self-degradation. Regarding large surface area catalysts, the glass-ceramics (GCs) with high formability, obtained by heat-treatment of the precursor glass, are plausible candidates. This study examines the photocatalytic behaviour of porous GCs obtained after acid leaching of MgO-TiO2-P2O5 GCs. After heat-treatment, anatase TiO2 was precipitated along with other phases. The diffraction intensity ratio between anatase and other phases was the maximum for a heat-treatment temperature of 900 °C. After acid leaching of the GCs, the relative surface area decreased with increasing TiO2 fraction; the surface area was also affected by the sample morphology. H2 generation was observed from porous GCs, while GCs without etching exhibited approximately zero activity. Thus, it was demonstrated that high surface area and prevention of the reduction reaction to Ti(III) are important for tailoring monolithic photocatalytic materials.

Excitation of coherent optical phonons in iron garnet by femtosecond laser pulses.

We employed femtosecond pump-probe technique to investigate the dynamics of coherent optical phonons in iron garnet. A phenomenological symmetry-based consideration reveals that oscillations of the terahertz T 2g mode are excited. Selective excitation by a linearly polarized pump and detection by a circularly polarized probe confirm that impulsive stimulated Raman scattering (ISRS) is the driving force for the coherent phonons. Experimental results obtained from ISRS measurements reveal excellent agreement with spontaneous Raman spectroscopy data, analyzed by considering the symmetry of the phonon modes and corresponding excitation and detection selection rules.

Boson peak dynamics of natural polymer starch investigated by terahertz time-domain spectroscopy and low-frequency Raman scattering.

Terahertz time-domain spectroscopy and low-frequency Raman scattering were performed on the natural polymer starch to investigate the boson peak (BP) dynamics. In the infrared spectrum, the BP was observed at 0.99THz at the lowest temperature. Compared to the result from a previous study for vitreous glucose, both the frequency of the BP and absorption coefficient show lower values than those of the vitreous glucose. These behaviors originate from the longer correlation length of the medium-range order and lower concentration of hydroxyl groups in the starch. In the Raman spectrum, the BP was observed at 1.1THz at room temperature, although the BP was not observed around room temperature due to the excess wing of the fast relaxation modes in the infrared spectrum. The temperature dependence of ε″(ν) during the heating process and cooling process shows a hysteresis below 230K. During the heating process, kinks were observed at 140K and 230K. These kinks are attributed to the ß-relaxation and the ßwet-relaxation, respectively.

Excitation of coupled spin-orbit dynamics in cobalt oxide by femtosecond laser pulses.

Ultrafast control of magnets using femtosecond light pulses attracts interest regarding applications and fundamental physics of magnetism. Antiferromagnets are promising materials with magnon frequencies extending into the terahertz range. Visible or near-infrared light interacts mainly with the electronic orbital angular momentum. In many magnets, however, in particular with iron-group ions, the orbital momentum is almost quenched by the crystal field. Thus, the interaction of magnons with light is hampered, because it is only mediated by weak unquenching of the orbital momentum by spin-orbit interactions. Here we report all-optical excitation of magnons with frequencies up to 9 THz in antiferromagnetic CoO with an unquenched orbital momentum. In CoO, magnon modes are coupled oscillations of spin and orbital momenta with comparable amplitudes. We demonstrate excitations of magnon modes by directly coupling light with electronic orbital angular momentum, providing possibilities to develop magneto-optical devices operating at several terahertz with high output-to-input ratio.Light pulses can control magnetism in a material, and the effective creation of magnetic oscillations leads to spintronic devices with higher efficiency. Here, the authors increase the efficiency of magnon excitation by using a material in which orbital angular momenta are not quenched.

Formation of metallic cation-oxygen network for anomalous thermal expansion coefficients in binary phosphate glass.

Understanding glass structure is still challenging due to the result of disorder, although novel materials design on the basis of atomistic structure has been strongly demanded. Here we report on the atomic structures of the zinc phosphate glass determined by reverse Monte Carlo modelling based on diffraction and spectroscopic data. The zinc-rich glass exhibits the network formed by ZnOx (averaged x<4) polyhedra. Although the elastic modulus, refractive index and glass transition temperature of the zinc phosphate glass monotonically increase with the amount of ZnO, we find for the first time that the thermal expansion coefficient is very sensitive to the substitution of the phosphate chain network by a network consisting of Zn-O units in zinc-rich glass. Our results imply that the control of the structure of intermediate groups may enable new functionalities in the design of oxide glass materials.

Fractal dynamics in a single crystal of a relaxor ferroelectric.

We report the high-resolution and broadband light-scattering spectroscopy of a single crystal of a prototypical relaxor ferroelectric, Pb(Mg(1/3)Nb(2/3))O(3). A self-similar broad central peak, whose intensity is expressed as I(ω) [Symbol: see text] ω(α) has been observed, indicating the presence of a fractal in the crystal. A strong correspondence exists between the temperature dependence of the exponent α and that of the reported behaviors of polar nanoregions. The estimated fractal dimension (d(f) ≈ 2.6) at low temperatures clearly indicates a percolation transition of the polar nanoregions at around 240 K.

Note: Higher resolution Brillouin spectroscopy by offset stabilization of a tandem Fabry-Pérot interferometer.

A simple modification to a Sandercock-type tandem Fabry-Pérot interferometer is demonstrated. By adding an independent reference laser with temperature tunability, narrow Brillouin lines that are tens GHz shifted from the Rayleigh line can be recorded with much higher frequency resolution than in the original system.

Second sound in SrTiO3.

We study collective phonon excitations in SrTiO3 by low-frequency light scattering. We employ extended thermodynamics for phonon gas to construct a theoretical spectral function that is applicable regardless of local thermal equilibrium. Our analysis reveals the temperature dependence of tauN, the relaxation time for the momentum-conserving phonon collisions (normal processes), in SrTiO3. These results indicate that the previously reported anomalous soundlike spectrum originates from second sound, which is a wavelike propagation of heat.

Measurement of polarization dependence of nonlinear susceptibility responsible for Rayleigh-wing and Brillouin scattering.

By using a simple optical geometry based on backward light scattering and employing a Sandercock-type tandem Fabry-Perot interferometer, we measure both the linear and the circular polarization dependences of Rayleigh-wing and Brillouin scattering in a sample of liquid-crystal 4-n-pentyl-4'-cyanobiphenyl. Observed polarization dependences are consistent with the third-order nonlinear susceptibilities, taking into account the traceless symmetric scattering tensor for Rayleigh-wing scattering and the isotropic scattering tensor for Brillouin scattering.