The
phase transition between gamma-trititanium-pentoxide (γ-Ti3O5) and delta-trititanium-pentoxide (δ-Ti3O5) was clarified from both experimental and theoretical
viewpoints. With decreasing temperature, the monoclinic I2/c crystal structure of γ-Ti3O5 was found to switch to a monoclinic P2/a crystal structure of δ-Ti3O5 due to lowering of symmetry. Electrical conductivity (σ) measurement
shows that γ-Ti3O5 behaves like a metallic
conductor with a σ value of 4.7 S cm–1 at
320 K, while δ-Ti3O5 shows a semiconductive
property with a σ value of 2.5 × 10–5 S cm–1 at 70 K. Optical measurement also supports
that γ-Ti3O5 is a metallic conductor,
while δ-Ti3O5 is a semiconductor with
a band gap of 0.07 eV. First-principles calculations show that γ-Ti3O5 is a metallic conductor, and the energy state
on the Fermi energy is composed of the 3d orbital of Ti and 2p orbital
of O with one-dimensional linkage along the crystallographic c-axis. On the contrary, δ-Ti3O5 has a band gap, and the energy state around the Fermi energy is
split into the valence band and the conduction band, which are assigned
to the lower and upper Hubbard bands, respectively. Thus, the phase
transition between γ-Ti3O5 and δ-Ti3O5 is caused by breaking of a one-dimensionally
conducting pathway due to a Mott–Hubbard metal–insulator
phase transition.
Ferrite magnets have a long history. They are used in motors, magnetic fluids, drug delivery systems, etc. Herein we report a mesoscopic ferrite bar magnet based on rod-shaped ε-Fe2O3 with a large coercive field (>25 kOe). The ε-Fe2O3–based bar magnet is a single crystal with a single magnetic domain along the longitudinal direction. A wide frequency range spectroscopic study shows that the crystallographic a-axis of ε-Fe2O3, which corresponds to the longitudinal direction of the bar magnet, plays an important role in linear and non-linear magneto-optical transitions, phonon modes, and the magnon (Kittel mode). Due to its multiferroic property, a magnetic-responsive non-linear optical sheet is manufactured as an application using an ε-Fe2O3–based bar magnet, resin, and polyethylene terephthalate. Furthermore, from the viewpoint of the large coercive field property, we demonstrate that a mesoscopic ε-Fe2O3 bar magnet can be used as a magnetic force microscopy probe.
A two-dimensional cyanide-bridged Co-W bimetal assembly, (HO)[Co(4-bromopyridine){W(CN)}], was prepared. A synchrotron radiation (SR) X-ray single-crystal measurement shows that the crystal structure is monoclinic in the P2/c space group. Magnetic and spectroscopic measurements show that this assembly takes Co(S = 0)-W(S = 0) in the temperature range of 2-390 K. Such a wide temperature range Co-W phase has not been reported so far. First-principles calculations show that the band gap is composed of a W valence band and a Co conduction band. 785 nm light irradiation causes photo-induced magnetization with a Curie temperature of 27 K and a coercive field of 2000 Oe. The crystal structure of the photo-induced phase was determined to have larger lattice constants in the two-dimensional layer (bc-plane) by 3% compared to the original phase, which is due to the expansion of the distance of Co-N. The photo-induced phase returns to the original phase upon thermal treatment. First-principles calculations, and magnetic, and optical measurements prove that this photomagnetism is caused by the optical charge-transfer-induced spin transition from Co(S = 0)-W(S = 0) to Co(S = 3/2)-W(S = 1/2).
Macroscopically oriented stable organic radicals have been obtained by using a liquid-crystalline (LC) gel composed of an l-isoleucine-based low molecular weight gelator containing a 2,2,6,6-tetramethylpiperidine 1-oxyl moiety. The LC gel has allowed magnetic measurements of the oriented organic radical. The gelator has formed fibrous aggregates in liquid crystals via intermolecular hydrogen bonds. The fibrous aggregates of the radical gelator are formed and oriented on cooling by applying a magnetic field to the mixture of liquid crystals and the gelator. Superconducting quantum interference device (SQUID) measurements have revealed that both oriented and nonoriented fibrous aggregates exhibited antiferromagnetic interactions, in which super-exchange interaction constant J is estimated as -0.89 cm(-1) .
A gel crystallization technique was successfully applied in the pioneering preparation of a single-crystalline form of the three-dimensional copper(II) octacyanidomolybdate(IV) network, which is a photomagnetic material. This assembly crystallizes with the formula {[Cu II
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