arXiv subjects

Takashi Tokushima

Publications and source records attributed to Takashi Tokushima.

4 recordsLinked to original sources

arXiv2026

Electronic excitations in the Shastry-Sutherland compound SrCu$_2$(BO$_3$)$_2$

SrCu2(BO3)2 (SCBO) is a paradigmatic realization of the Shastry-Sutherland model, hosting geometrically frustrated spin dimers and a variety of quantum magnetic phases and phenomena. Although its magnetic properties have been extensively studied, the high-energy electronic excitations that determine the crystal-field environment and Cu-O hybridization have remained largely unexplored. Here we combine Cu L3-edge resonant inelastic x-ray scattering (RIXS), broadband optical spectroscopy, and electronic-structure calculations to determine the relevant local and interband excitation energy scales in SCBO. RIXS resolves a well-defined manifold of localized Cu2+ d-d excitations between 1.8 and 2.4 eV, whose energies and polarization dependence are well reproduced by multireference quantum-chemistry calculations. In contrast, optical spectroscopy identifies charge-transfer excitations with an absorption onset near 1.2-1.6 eV and a broader higher-energy structure around 4.5 eV, which are qualitatively captured by DFT+U calculations. Taken together, these results define the characteristic energy scales of d-d and CT excitations, offering quantitative benchmarks for computational frameworks and providing essential input for refining superexchange-based magnetic models of this prototypical frustrated quantum antiferromagnet.

cond-mat.str-el↗

arXiv2025

Intermolecular Radiative Decay: A non-local decay mechanism providing an insider's view of the solvation shell

Aqueous solutions are crucial in chemistry, biology, environmental science, and technology. The chemistry of solutes is influenced by the surrounding solvation shell of water molecules, which have different chemical properties than bulk water due to their different electronic and geometric structure. It is an experimental challenge to selectively investigate this property-determining electronic and geometric structure. Here, we report experimental results on a novel non-local X-ray emission process, Intermolecular Radiative Decay (IRD), for the prototypical ions Na$^{+}$ and Mg$^{2+}$ in water. We show that, in IRD, an electron from the solvation shell fills a core hole in the solute, and the released energy is emitted as an X-ray photon. We analyze the underlying mechanism using theoretical calculations, and show how IRD will allow us to meet the challenge of chemically selective probing of solvation shells from within.

physics.chem-ph↗

arXiv2019

Characterization of in-gap states in epitaxial CoFe2O4(111) layers grown on Al2O3(111)/Si(111) by resonant inelastic x-ray scattering

We have studied in-gap states in epitaxial CoFe2O4(111), which potentially acts as a perfect spin filter, grown on a Al2O3(111)/Si(111) structure by using ellipsometry, Fe L2,3-edge x-ray absorption spectroscopy (XAS), and Fe L2,3-edge resonant inelastic x-ray scattering (RIXS), and revealed the relation between the in-gap states and chemical defects due to the Fe2+ cations at the octahedral sites (Fe2+ (Oh) cations). The ellipsometry measurements showed the indirect band gap of 1.24 eV for the CoFe2O4 layer and the Fe L2,3-edge XAS confirmed the characteristic photon energy for the preferential excitation of the Fe2+ (Oh) cations. In the Fe L3-edge RIXS spectra, a band-gap excitation and an excitation whose energy is smaller than the band-gap energy (Eg = 1.24 eV) of CoF2O4, which we refer to as "below-band-gap excitation (BBGE)" hereafter, were observed. The intensity of the BBGE was strengthened at the preferential excitation energy of the Fe2+ (Oh) cations. In addition, the intensity of the BBGE was significantly increased when the thickness of the CoFe2O4 layer was decreased from 11 to 1.4 nm, which coincides with the increase in the site occupancy of the Fe2+ (Oh) cations with decreasing the thickness. These results indicate that the BBGE comes from the in-gap states of the Fe2+ (Oh) cations whose density increases near the heterointerface on the bottom Al2O3 layer. We have demonstrated that RIXS measurements and analyses in combination with ellipsometry and XAS are effective to provide an insight into in-gap states in thin-film oxide heterostructures.

cond-mat.mtrl-sci↗

arXiv2018

Quasi-free-standing monolayer hexagonal boron nitride on Ni

The electronic structure of monolayer hexagonal boron nitride grown on Ni by the diffusion and precipitation method was studied by x-ray absorption spectroscopy, emission spectroscopy, x-ray photoelectron spectroscopy and micro-ultraviolet photoemission spectroscopy. No indication of hybridization between h-BN pi and Ni 3d orbitals was observed. That is, the monolayer h-BN was found to be in the quasi-free-standing state. These results are in striking contrast to those of previous studies in which h-BN was strongly bound to the Ni surface by the orbital hybridization. The absence of hybridization is attributed to absence of a Ni(111) surface in this study. The lattice-matched Ni(111) surface is considered to be essential to orbital hybridization between h-BN and Ni.

cond-mat.mes-hall↗