arXiv subjects

T. D. Kuehne

Publications and source records attributed to T. D. Kuehne.

6 recordsLinked to original sources

arXiv2026

Electronic-Entropy-Driven Phase Transitions in Compressed Iron Oxides

Electronic entropy is usually treated as a secondary correction to structural stability, but under strong electronic excitation it can become a primary thermodynamic driving force. Here we show that electronic entropy can drive both polymorphic and stoichiometric phase transformations in compressed iron oxides. Using finite-temperature density functional theory, we calculate the electronic-temperature-dependent Gibbs free energies of Fe$_2$O, FeO, Fe$_4$O$_5$, Fe$_3$O$_4$, and multiple Fe$_2$O$_3$ polymorphs, including $α$-, $ι$-, $ζ$-, $η$-, and $θ$-Fe$_2$O$_3$, over the pressure range 60--260 GPa. At 60-140 GPa, electronic excitation mainly reorganizes the relative stability of Fe$_2$O$_3$ polymorphs, driving transitions from $ι$-Fe$_2$O$_3$ to $η$-Fe$_2$O$_3$. At 180 GPa, the free-energy landscape becomes strongly competitive as FeO is stabilized over an intermediate range of electronic temperature, while $η$-Fe$_2$O$_3$ becomes favourable at higher T. At 220-260 GPa, the lowest-free-energy phase at low T is the Fe-rich compound Fe$_2$O, but increasing electronic temperature stabilizes FeO. These results demonstrate that electronic entropy can control not only the relative stability of crystal structures at fixed composition, but also the competition between different iron-oxide stoichiometries. The predicted electronic-entropy-driven phase boundaries provide a route to nonthermal structural transformations in ultrafast and high-energy-density experiments.

cond-mat.mtrl-sci↗

arXiv2026

From Entropy to Compression: Competing Thermodynamic Drivers of Structural Transitions in Transition Metals

Solid-solid phase transitions in metals are traditionally driven by changes in density or external pressure. Here we show that, under strong electronic excitation, structural stability is governed by the interplay between electronic effects and compression. Using finite-temperature density functional theory, we construct pressure-temperature phase diagrams for 15 metals spanning hcp-, fcc-, and bcc-ground-state structures. The results reveal a systematic reduction of structural diversity with increasing electronic temperature, with stability increasingly dominated by the fcc structure, while hcp remains a persistent secondary phase and bcc stability is progressively suppressed. At elevated temperatures, fcc is broadly favored, whereas bcc is stabilized primarily by compression, leading to a material-dependent competition across the periodic table. These findings provide a unified framework for understanding structural transformations in electronically excited metals and highlight the importance of considering both electronic excitation and pressure in describing phase stability far from equilibrium.

cond-mat.mtrl-sci↗

arXiv2026

Electronic-Entropy-Driven Solid-Solid Phase Transitions in Elemental Metals

We compute the thermodynamic phase diagram of seventeen elemental metals with hexagonal close-packed (hcp), face-centered cubic (fcc), and body-centered cubic (bcc) crystal structures using finite-temperature density functional theory. Helmholtz free-energy differences between competing hcp, fcc, and bcc phases are evaluated as functions of electronic temperature up to 7 eV, allowing us to identify solid-solid phase transitions driven by electronic entropy. The systems studied include Zr, Ti, Cd, Zn, Co, and Mg (hcp), Ni, Cu, Ag, Al, Pt, and Pb (fcc), and Cr, W, V, Nb, and Mo (bcc) in their ground-state structures. From the free-energy crossings, we extract the transition electronic temperatures and analyze systematic trends across the metallic systems. We found that all the studied systems go through one or two solid-solid phase transition caused purely by electronic entropy except Mg and Pb. Our results establish electronic entropy as a key factor governing structural stability in metals under strong electronic excitation.

cond-mat.mtrl-sci↗

arXiv2019

Unconventional phase III of high-pressure solid hydrogen

We reassess the phase diagram of high-pressure solid hydrogen using mean-field and many-body wave function based approaches to determine the nature of phase III of solid hydrogen. To discover the best candidates for phase III, density functional theory calculations within the meta-generalized gradient approximation by means of the strongly constrained and appropriately normed (SCAN) semilocal density functional are employed. We study eleven molecular structures with different symmetries, which are the most competitive phases, within the pressure range of 100 to 500~GPa. The SCAN phase diagram predicts that the $C2/c-24$ and $P6_122-36$ structures are the best candidates for phase III with an energy difference of less than 1~meV/atom. To verify the stability of the competitive insulator structures of $C2/c-24$ and $P6_122-36$, we apply the diffusion Monte Carlo (DMC) method to optimise the percentage $α$ of exact-exchange in the trial many-body wave function. We found that the optimised $α$ equals to $40 \%$, and denote the corresponding exchange and correlation functional as PBE1. The energy gain with respect to the well-known hybrid functional PBE0, where $α= 25\%$, varies with density and structure. The PBE1-DMC enthalpy-pressure phase diagram predicts that the $P6_122-36$ structure is stable up to 210~GPa, where it transforms to the $C2/c-24$. Hence, we predict that the phase III of high-pressure solid hydrogen is polymorphic.

cond-mat.other↗

arXiv2013

Quantum Monte Carlo Study of High Pressure Solid Molecular Hydrogen

We use the diffusion quantum Monte Carlo (DMC) method to calculate the ground state phase diagram of solid molecular hydrogen and examine the stability of the most important insulating phases relative to metallic crystalline molecular hydrogen. We develop a new method to account for finite-size errors by combining the use of twist-averaged boundary conditions with corrections obtained using the Kwee-Zhang-Krakauer (KZK) functional in density functional theory. To study band-gap closure and find the metallization pressure, we perform accurate quasi-particle many-body calculations using the $GW$ method. In the static approximation, our DMC simulations indicate a transition from the insulating Cmca-12 structure to the metallic Cmca structure at around 375 GPa. The $GW$ band gap of Cmca-12 closes at roughly the same pressure. In the dynamic DMC phase diagram, which includes the effects of zero-point energy, the Cmca-12 structure remains stable up to 430 GPa, well above the pressure at which the $GW$ band gap closes. Our results predict that the semimetallic state observed experimentally at around 360 GPa [Phys. Rev. Lett. {\bf 108}, 146402 (2012)] may correspond to the Cmca-12 structure near the pressure at which the band gap closes. The dynamic DMC phase diagram indicates that the hexagonal close packed $P6_3/m$ structure, which has the largest band gap of the insulating structures considered, is stable up to 220 GPa. This is consistent with recent X-ray data taken at pressures up to 183 GPa [Phys. Rev. B {\bf 82}, 060101(R) (2010)], which also reported a hexagonal close packed arrangement of hydrogen molecules.

cond-mat.mtrl-sci↗

arXiv2008

Coexistence of tetrahedral and octahedral-like sites in amorphous phase change materials

Chalcogenide alloys are materials of interest for optical recording and non-volatile memories. We perform ab-initio molecular dynamics simulations aiming at shading light onto the structure of amorphous Ge2Sb2Te5 (GST), the prototypical material in this class. First principles simulations show that amorphous GST obtained by quenching from the liquid phase displays two types of short range order. One third of Ge atoms are in a tetrahedral environment while the remaining Ge, Sb and Te atoms display a defective octahedral environment, reminiscent of cubic crystalline GST.

cond-mat.mtrl-sci↗