arXiv subjects

Yoshiyuki Kawazoe

Publications and source records attributed to Yoshiyuki Kawazoe.

At least 19 recordsLinked to original sources

arXiv2026

Ab initio Phase Diagram of Ta2O5

Tantalum pentoxide (Ta2O5) is a polymorphic wide-bandgap semiconductor with outstanding dielectric properties and widespread use in optical and electronic technologies. Its rich structural diversity, arising from multiple polymorphs accessible under different synthesis conditions, has made Ta2O5 a long-standing subject of interest. However, a unified understanding of the thermodynamic stability and phase transitions of its polymorphs across pressure-temperature (P-T) space has remained elusive. Here, using first-principles calculations, we map the thermodynamic landscape of Ta2O5 and establish a comprehensive P-T phase diagram together with a phase-stability hierarchy. We find that Gamma-Ta2O5 and B-Ta2O5 dominate the phase diagram over a broad range of P-T conditions: Gamma-Ta2O5 is stabilized at low pressures, while B-Ta2O5 becomes thermodynamically favored at higher pressures up to ~ 60 GPa, beyond which Y-Ta2O5 emerges as the most stable phase. Crucially, the zero-point energy (ZPE), one aspect of nuclear quantum effects (NQEs), plays a significant role in determining relative phase stability, contributing substantially to the Gibbs free energy and altering phase boundaries. A re-entrant phase transition between Gamma and B-Ta2O5 is predicted near ~ 2 GPa, revealing unexpected complexity in the phase behavior of this oxide. More generally, we identify a characteristic temperature (T_0), at which zero-point and thermal phonon contributions to the free energy become comparable, and show that T_0 is approximately one-third of the Debye temperature. This relationship provides a simple, physically transparent criterion for assessing the importance of NQEs in phase stability, with implications extending beyond Ta2O5 to a broad class of complex oxides.

cond-mat.mtrl-sci↗

arXiv2026

An Efficient Method for Gibbs Free Energy Evaluation under Volume Compression

Accurate evaluation of Gibbs free energies is essential for constructing pressure-temperature phase diagrams. Conventional methods based on the quasi-harmonic approximation (QHA) require phonon spectra at many volume points and are therefore expensive in general. Here we develop an efficient method based on the interpolation of a few ab initio data points for Gibbs free energy evaluation under volume compression. Phonon spectra are calculated only at selected volumes. An effective Gruneisen parameter derived from the zero-point energy (ZPE) reconstructs the static-ZPE branch, while piecewise mode-resolved Gruneisen slopes reconstruct the finite-temperature vibrational branches on the target volume grids. The method is validated against QHA benchmarks for diamond (C), Al, Si, Ge, rutile TiO2, beta-PtO2, and Ta2O5 polymorphs. For simple benchmark systems (C, Al, Si, Ge, rutile TiO2, and beta-PtO2), the Gibbs free energy mean absolute errors (MAEs) relative to the QHA benchmarks remain below 0.53 meV/atom, with a six-system average of 0.148 meV/atom, while the number of explicit phonon volume points is reduced from about 20-21 to 3 in the lowest-cost implementation. For the more complex Ta2O5 polymorphs, the reconstructed free energies reproduce the main phase-stability topology despite larger phase-dependent errors. With reference to the QHA workflows, the interpolation method in this work achieves speedups of 5.911-9.023 times and remains reliable for moderate compression ranges where phonon frequencies vary smoothly with volume.

cond-mat.mtrl-sci↗

arXiv2025

Unveiling two-dimensional electron systems on ultra-wide bandgap semiconductor $\mathrmβ$-Ga$_2$O$_3$

Ultra-wide bandgap (UWBG) semiconductors promise to revolutionize power electronics, yet a fundamental understanding of their interfacial electronic structure has been hindered by the absence of direct experimental observation. Here, we report the first momentum-resolved observation of two-dimensional electron systems on a UWBG material, enabled by angle resolved photoemission spectroscopy (ARPES) on high-purity $β$-Ga$_2$O$_3$ single crystals. Alkaline-metal-induced electron doping forms an isotropic circular Fermi surface, achieving a sheet carrier density of up to $1.0\times10^{14}$ $\mathrm{cm}^{-2}$. Self-consistent Poisson-Schrödinger calculations show that the electrons are confined within 1.2 nm of the surface and reveal an internal electric field of $18$ MV cm$^{-1}$. Crucially, our measurements reveal a pronounced renormalization of the electronic band structure: a series of carrier-density-dependent ARPES measurements shows that as the carrier density increases from $2\times10^{13}$ to $1.0\times10^{14}$ $\mathrm{cm}^{-2}$, the effective mass anomalously increases, nearly doubling to a final value of 0.48 $\textit{m}_{\mathrm{e}}$. This trend is notably opposite to that reported for other oxide semiconductors, pointing towards a unique renormalization mechanism in $β$-Ga$_2$O$_3$. Our findings establish the interfacial electronic structure of $β$-Ga$_2$O$_3$ and demonstrate that UWBG materials provide fertile ground for exploring carrier-density-driven electronic phenomena, opening new avenues for future quantum and power devices.

cond-mat.mtrl-sci↗

arXiv2025

Possible Orthorhombic Phase of Ta$_2$O$_5$ under High Pressures

A potential orthorhombic phase of Ta$_2$O$_5$, designated as Y-Ta$_2$O$_5$, is predicted under high-pressure conditions through density functional theory (DFT) calculations combined with structural search algorithms. This phase, consisting of four formula units per unit cell ($Z = 4$), exhibits the highest known Ta-O coordination numbers. Y-Ta$_2$O$_5$ is found to be the most energetically favorable form of Ta$_2$O$_5$ in the pressure range of approximately 70 GPa to at least 200 GPa. Both standard DFT-GGA and higher-accuracy GW calculations reveal that Y-Ta$_2$O$_5$ is a wide bandgap semiconductor with a direct bandgap. Additionally, nuclear quantum effects (NQEs) introduce nontrivial corrections to external pressure at fixed volumes, underscoring their significance in high-pressure phase stability analyses.

cond-mat.mtrl-sci↗

arXiv2022

Computational Search for Two-Dimensional Photocatalysts

To overcome current serious energy and environmental issues, photocatalytic water splitting holds great promise because it requires only solar energy as an energy input to produce hydrogen. Two-dimensional (2D) semiconductors and heterostructures possess several inherent advantages which are more suitable for boosting solar energy than their bulk counterparts. In this work, by performing high-throughput first-principles calculations combined with a semiempirical van der Waals dispersion correction, we first provided the periodic table of band alignment type for van der Waals heterostructures when packing any two of the 260 semiconductor monolayers obtained from our 2D semiconductor database (2DSdb) (https://materialsdb.cn/2dsdb/index.html). Based on the rules of thumb for photocatalytic water splitting, we have further screened dozens of potential semiconductors and thousands of heterostructures which are promising for photocatalytic water splitting. The resulting database would provide a useful guidance for experimentalists to design suitable 2D vdWHs and photocatalysts according to desired applications.

cond-mat.mtrl-sci↗

arXiv2022

High-Throughput Computational Screening of Two-Dimensional Semiconductors

By performing high-throughput first-principles calculations combined with a semiempirical van der Waals dispersion correction, we have screened 74 direct- and 185 indirect-gap two dimensional (2D) nonmagnetic semiconductors from near 1000 monolayers according to the criteria for energetic, thermodynamic, mechanical, dynamic and thermal stabilities, and conductivity type. We present the calculated lattice constants, simulated scanning tunnel microscopy, formation energy, Young's modulus, Poisson's ratio, shear modulus, anisotropic effective mass, band structure, band gap, ionization energy, and electron affinity for each candidate meeting our criteria. The resulting 2D semiconductor database (2DSdb) can be accessed via the website https://materialsdb.cn/2dsdb/index.html. The 2DSdb provides an ideal platform for computational modeling and design of new 2D semiconductors and heterostructures in photocatalysis, nanoscale devices, and other applications. Further, a linear fitting model was proposed to evaluate band gap, ionization energy and electron affinity of semiconductor from the density functional theory (DFT) calculated data as initial input. This model can be as precise as hybrid DFT but with much lower computational cost.

cond-mat.mes-hall↗

arXiv2020

Topological Phase Transition Induced by Image Potential States in MXenes: A Theoretical Investigation

MXenes, a family of two-dimensional transition metal carbides and nitrides, have various tunable physical and chemical properties. Their diverse prospective applications in electronics and energy storage devices have triggered great interests in science and technology. MXenes can be functionalized by different surface terminations. Some O and F functionalized MXenes monolayers have been predicted to be topological insulators (TIs). However, the reported OH functionalized MXenes TIs are very few and their electronic structures need to be investigated in more detail. It has been revealed that the work functions of MXenes are reduced significantly by OH termination and the image potential (IP) states move close to the Fermi level. The wave functions of these IP states are spatially extensive outside the surfaces. By stacking the OH-functionalized MXenes, the energies of the IP states can be modulated by the interlayer distances of multilayers, because the overlap and hybridization of the wave functions between the neighboring layers are significant. Therefore, these stacking layers are interacted and coupled with IP states. Here, based on first-principles calculations, we demonstrate that the stacking of two-dimensional topologically trivial OH-functionalized MXenes, such as V$_2$HfC$_2$(OH)$_2$, possibly gives rise to the topologically nontrivial energy bands. In other words, the topological properties of V$_2$HfC$_2$(OH)$_2$ multilayers can be modulated by its interlayer distance. An energy band inversion involving IP states is proposed. We expect that these results can advance the future application of MXenes or other low work function multilayer materials as controllable TI devices.

cond-mat.mtrl-sci↗

arXiv2020

Modulation of Nearly Free Electron States in Hydroxyl-Functionalized MXenes: A First-Principles Study

The transition metal carbides (namely MXenes) and their functionalized derivatives exhibit various physical and chemical characteristics and offer many potential applications in electronic devices and sensors. Using density functional theory (DFT), it is revealed that the nearly free electron (NFE) states are near the Fermi levels in hydroxyl (OH) functionalized MXenes. Most of the OH-terminated MXene are metallic, but some of them, e.g. Sc2C(OH)2, are semiconductors and the NFE states are conduction bands. In this paper, to investigate the NFE states in MXenes, an attractive image-potential well model is adopted. Compared the solutions of this model with the DFT calculations, it is found that due to the overlap of spatially extensive wave functions of NFE states and their hybridization between the artificial neighboring layers imposed by the periodical boundary conditions (PBCs), the DFT results represent the properties of multiple layers, intrinsically. Based on the DFT calculations, it is found that the energy gap widths are affected by the interlayer distances. We address that the energetics of the NFE states can be modulated by the external electric fields and it is possible to convert semiconducting MXenes into metals. This band-gap manipulation makes the OH-terminated semiconducting MXenes an excellent candidate for electronic switch applications. Finally, using a set of electron transport calculations, I-V characteristics of Sc2C(OH)2 devices are investigated with the gate voltages.

cond-mat.mes-hall↗

arXiv2019

Adsorption and Diffusion of H Atoms on beta-PtO2 Surface: The Role of Nuclear Quantum Effects

The adsorption and diffusion of H atoms on beta-PtO2(001) surface have been studied using first-principles calculations. The chemisorbed H atoms are found to bind preferentially on the top sites of O atoms due to the much larger adsorption energies with comparison to adsorption atop Pt atoms. The calculated energy barriers along the optimal diffusion paths are comparable with that of H diffusion on Pt(111). Within the WKB approximation, the nuclear quantum effects (NQEs) along the diffusion paths are investigated. It turns out that the NQEs are significant for the surface diffusion of H at room temperature and play a dominant role in cryogenic conditions.

cond-mat.mtrl-sci↗

arXiv2019

Transformation of hydrogen bond network during the CO2 clathrate hydrate dissociation

The object of this study is the kinetic process of solid-liquid first-order phase transition - melting of carbon dioxide CS-I hydrate with various cavity occupation ratios. The work was done within a framework of study on the local structure of water molecules. These include the time depending change of the short-range order at temperatures close to the melting point and comparison with hexagonal ice structure. Using molecular dynamics method, dependencies of the internal energy of the studied systems on the time of heating were found. Jumps in the internal energy of solids in the range at 275-300 K indicate a phase transition. The study of oxygen-oxygen radial distribution and hydrogen-oxygen-oxygen mutual orientation angles between molecules detached at no more than 3.2 angstroms allowed to find the H-bond coordination number of all molecules and full number of H-bonds and showed the instant (less than 1 nanosecond) reorganization of short-range order of all molecules. The structure analysis of every neighbor water molecules pairs showed the ~10-15 percents decrease of H-bond number after the melting whereas all molecules form single long-range hydrogen bond network. The analysis of hydrogen bond network showed the minor changes in the H-bond interaction energy at solid-liquid phase transition.

cond-mat.mtrl-sci↗

arXiv2018

Adsorption of Water on Fluorinated Graphene

In this paper, we investigate the adsorption of water monomer on fluorinated graphene using state-of-the-art first principles methods within the framework of density functional theory (DFT). Four different methods are employed to describe the interactions between water and the carbon surface: The traditional DFT calculations within the generalized gradient approximation (GGA), and three types of calculations using respectively the semi-empirical DFT-D2method, the original van der Waals density functional (vdW-DF) method, and one of its variants. Compared with the adsorption on pristine graphene, the adsorption energies of water on fluorinated graphene are significantly increased, and the orientations of water diploe moment are notably changed. The most stable configuration is found to stay right above the top site of the C atom which is bonded with F, and the dipole moment of water molecule aligns spontaneously along the surface normal.

cond-mat.mtrl-sci↗

arXiv2018

Adsorption and Diffusion of F2 molecules on Pristine Graphene

The adsorption and diffusion of F2 molecules on pristine graphene have been studied using first-principles calculations. For the diffusion of F2 from molecular state in gas phase to the dissociative adsorption state on graphene surface, a kinetic barrier is identified, which explains the inertness of graphene in molecular F2 at room temperature, and its reactivity with F2 at higher temperatures. Studies on the diffusion of F2 molecules on graphene surface determine the energy barriers along the optimal diffusion pathways, which help to understand the high stability of fluorographene.

cond-mat.mtrl-sci↗

arXiv2018

Prediction of New Ground State Crystal Structure of Ta2O5

Tantalum pentoxide (Ta2O5) is a wide-gap semiconductor which has important technological applications. Despite the enormous efforts from both experimental and theoretical studies, the ground state crystal structure of Ta2O5 is not yet uniquely determined. Based on first-principles calculations in combination with evolutionary algorithm, we identify a triclinic phase of Ta2O5, which is energetically much more stable than any phases or structural models reported previously. Characterization of the static and dynamical properties of the new phase reveals the common features shared with previous metastable phases of Ta2O5. In particular, we show that the d-spacing of ~ 3.8 Å found in the X-ray diffraction (XRD) patterns of many previous experimental works, is actually the radius of the second Ta-Ta coordination shell as defined by radial distribution functions.

cond-mat.mtrl-sci↗

arXiv2017

New carbon allotropes in sp + sp$^3$ bonding networks consisting of C$_8$ cubes

We identify by ab initio calculations a new type of three-dimensional carbon allotropes constructed by inserting acetylenic or diacetylenic bonds into a body-centered cubic C$_8$ lattice. The resulting $sp+sp^3$-hybridized cubane-yne and cubane-diyne structures consisting of C$_8$ cubes can be characterized as a cubic crystalline modification of linear carbon chains, but energetically more favorable than the simplest linear carbyne chain and the cubic tetrahedral diamond and yne-diamond consisting of C$_4$ tetrahedrons. Electronic band calculations indicate that these new carbon allotropes are semiconductors with an indirect band gap of 3.08 eV for cubane-yne and 2.53 eV for cubane-diyne. The present results establish a new type of carbon phases consisting of C$_8$ cubes and offer insights into their outstanding structural and electronic properties.

cond-mat.mtrl-sci↗

arXiv2017

Theoretical Prediction of Two-Dimensional Functionalized MXene Nitrides as Topological Insulators

Recently, two-dimensional (2D) transition metal carbides and nitrides, namely, MXenes have attracted lots of attention for electronic and energy storage applications. Due to a large spin-orbit coupling (SOC) and the existence of a Dirac-like band at the Fermi energy, it has been theoretically proposed that some of the MXenes will be topological insulators (TIs). Up to now, all of the predicted TI MXenes belong to transition metal carbides, whose transition metal atom is W, Mo or Cr. Here, on the basis of first-principles and Z2 index calculations, we demonstrate that some of the MXene nitrides can also be TIs. We find that Ti3N2F2 is a 2D TI, whereas Zr3N2F2 is a semimetal with nontrivial band topology and can be turned into a 2D TI when the lattice is stretched. We also find that the tensile strain can convert Hf3N2F2 semiconductor into a 2D TI. Since Ti is one of the mostly used transition metal element in the synthesized MXenes, we expect that our prediction can advance the future application of MXenes as TI devices.

cond-mat.mes-hall↗

arXiv2017

Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters

We have carried out a density functional theory study on the structures of DMSO clusters and analysed the structure and their stability using molecular electrostatic potential and quantum theory of atoms-in-molecules (QTAIM). The ground state geometry of the DMSO clusters, prefer to exist in ouroboros shape. Pair wise interaction energy calculation show the interaction between methyl groups of adjacent DMSO molecules and a destabilization is is created by the methyl groups which are away from each other. Molecular electrostatic potential analysis shows the existence of hole on the odd numbered clusters, which helps in their highly directional growth. QTAIM analysis show the existence of two intermolecular hydrogen bonds, of type SOC hydrogen bonds and methyl CHC dihydrogen bonds. The computed and Laplacian values were all positive for the intermolecular bonds, supporting the existence of noncovalent interactions. The computed ellipticity for the dihydrogen bonds have values > 2, which confirms the delocalization of electron, are mainly due to the hydrogen-hydrogen interactions of methyl groups. A plot of total hydrogen bonding energy vs the observed total local electron density shows linearity with correlation coefficient of near unity, which indicates the cooperative effects of intermolecular dihydrogen HH bonds.

physics.chem-ph↗

arXiv2017

Chemical reaction directed oriented attachment: from precursor particles to new substances

The oriented attachment (OA) of nanoparticles is an important mechanism for the synthesis of the crystals of inorganic functional materials, and the formation of natural minerals. For years it has been generally acknowledged that OA is a physical process, i.e., particle alignments and interface fusion via mass diffusion, not involving the formation of new substances. Hence, the obtained crystals maintain identical crystallographic structures and chemical constituents to those of the precursor particles. Here we report a chemical reaction directed OA growth, through which Y2(CO3)3.2H2O nanoparticles are converted to single-crystalline double-carbonates (e.g., NaY(CO3)2.6H2O). The dominant role of OA growth is supported by our first-principles calculations. Such a new OA mechanism enriches the aggregation-based crystal growth theory.

cond-mat.mtrl-sci↗

arXiv2016

Multiple Unpinned Dirac Points in Group-Va Single-layers with Phosphorene Structure

Emergent Dirac fermion states underlie many intriguing properties of graphene, and the search for them constitute one strong motivation to explore two-dimensional (2D) allotropes of other elements. Phosphorene, the ultrathin layers of black phosphorous, has been a subject of intense investigations recently, and it was found that other group-Va elements could also form 2D layers with similar puckered lattice structure. Here, by a close examination of their electronic band structure evolution, we discover two types of Dirac fermion states emerging in the low-energy spectrum. One pair of (type-I) Dirac points is sitting on high-symmetry lines, while two pairs of (type-II) Dirac points are located at generic $k$-points, with different anisotropic dispersions determined by the reduced symmetries at their locations. Such fully-unpinned (type-II) 2D Dirac points are discovered for the first time. In the absence of spin-orbit coupling, we find that each Dirac node is protected by the sublattice symmetry from gap opening, which is in turn ensured by any one of three point group symmetries. The spin-orbit coupling generally gaps the Dirac nodes, and for the type-I case, this drives the system into a quantum spin Hall insulator phase. We suggest possible ways to realize the unpinned Dirac points in strained phosphorene.

cond-mat.mtrl-sci↗