Ab initio study of metastable occupation of tetrahedral sites in palladium hydrides and its impact on superconductivity

A recent experimental work on palladium hydrides suggested that metastable structures with hydrogen atoms occupying tetrahedral sites could lead to superconductivity above 50 K, a huge increase compared to the 9 K critical temperature of the stable structure with all hydrogen atoms occupying octahedral sites. By generating many structures with hydrogen atoms randomly occupying the octahedral and tetrahedral sites of the face-centered-cubic lattice and calculating their energy at different theoretical levels from first principles, we determine that metastable structures with partial or full occupation of tetrahedral sites are possible, even when the ionic quantum zero-point energy and anharmonicity are included in the calculations. Anharmonicity is crucial in palladium hydrides when hydrogen atoms occupy octahedral sites and, in fact, makes the structure with full octahedral occupation the ground state. Despite the metastable existence of structures with full or partial tetrahedral site occupation, the superconducting critical temperature is reduced with the number of tetrahedral sites occupied. Our calculations discard that the occupation of tetrahedral sites can increase the critical temperature in palladium hydrides.Funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 802533

Absence of sizable superconductivity in hydrogen boride: A first-principles study

The recently synthesized hydrogen boride monolayer in the Cmmm phase is a promising superconductor due to its similarity to MgB2 and the large hydrogen content in its structure. Making use of first-principles calculations based on density functional theory, we study its electronic, vibrational, and superconducting properties and conclude that despite the expectations, hydrogen boride does not have a sizable superconducting critical temperature. The presence of hydrogen in the system alters the boron-boron bonding, weakening the electron-phonon interaction. We have studied the effect of enhancing the critical temperature by doping the system, but the inclusion of electrons or holes reveals this to be ineffective. We attribute the small critical temperature of this system to the vanishing hydrogen character of the states at the Fermi level, which are dominated by boron p states. Our results hint at a possible relation between the presence of a large proportion of hydrogenlike states at the Fermi level and a large superconducting critical temperature in hydrogenated monolayers.Funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 802533)

Impact of ionic quantum fluctuations on the thermodynamic stability and superconductivity of LaBH8

The recent prediction of a metastable high-symmetry Fm-3m phase of LaBH8 gives hopes to reach high superconducting critical temperatures at affordable pressures among ternary hydrogen-rich compounds. Making use of first-principles calculations within density functional theory and the stochastic self-consistent harmonic approximation, we determine that ionic quantum fluctuations drive the system dynamically unstable below 77 GPa, a much higher pressure than the 45 GPa expected classically. Quantum anharmonic effects stretch the covalent B-H bond in the BH8 units of the structure, and consequently, soften all hydrogen-character modes. Above 77 GPa Fm-3m LaBH8 remains metastable, and interestingly, its superconducting critical temperature is largely enhanced by quantum anharmonic effects, reaching critical temperatures around 160 K at the verge of the dynamical instability. Our results suggest that low-pressure metastable phases with covalently bonded symmetric XH8 units will be destabilized by ionic quantum fluctuations.This research was supported by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant Agreement No. 802533). We acknowledge PRACE for awarding us access to Joliot-Curie Rome at TGCC, France

Black metal hydrogen above 360 GPa driven by proton quantum fluctuations

Hydrogen metallization under stable conditions is a major quest for realizing the first room temperature su- perconductor. Recent low-temperature experiments report different metallization pressures, varying from 360GPa to 490GPa. In this work, we simulate structural properties, vibrational Raman, IR and optical spectra of hydrogen phase III accounting for proton quantum effects. We demonstrate that nuclear quantum fluctuations downshift the vibron frequencies by 25%, introduce a broad line-shape in the Raman spectra, and reduce the optical gap by 3eV. We show that hydrogen metallization occurs at 380GPa in phase III due to band overlap, in good agreement with transport data. Our simulations predict this state is a black metal - transparent in the IR - so that the shiny metal observed at 490GPa is not phase III. We predict the conductivity onset and the optical gap will substantially increase if hydrogen is replaced by deuterium, underlining that metallization is driven by quantum fluctuations and is thus isotope dependent. We show how hydrogen acquires conductivity and brightness at different pressures, explaining the apparent contradictions in existing experimental scenarios.European Research Council (ERC) under the European Unions Horizon 2020 research and innovation program (grant agreement No. 802533

Strong anharmonic and quantum effects in Pm-3n AlH3 under high pressure: A first-principles study

Motivated by the absence of experimental superconductivity in the metallic Pm-3n phase of AlH3 despite the predictions, we reanalyze its vibrational and superconducting properties at pressures P≥99 GPa making use of first-principles techniques. In our calculations based on the self-consistent harmonic approximation method that treats anharmonicity beyond perturbation theory, we predict a strong anharmonic correction to the phonon spectra and demonstrate that the superconducting critical temperatures predicted in previous calculations based on the harmonic approximation are strongly suppressed by anharmonicity. The electron-phonon coupling concentrates on the lowest-energy hydrogen-character optical modes at the X point of the Brillouin zone. As a consequence of the strong anharmonic enhancement of their frequency, the electron-phonon coupling is suppressed by at least 30%. The suppression in λ makes Tc smaller than 4.2 K above 120 GPa, which is well consistent with the experimental evidence. Our results underline that metal hydrides with hydrogen atoms in interstitial sites are subject to huge anharmonic effects.This research was supported by the European Research Council (ERC) under the European Unions Horizon 2020 research and innovation programme (grant agreement No. 802533). R. B. thankfully acknowledges the computer resources at Altamira and the technical support provided by Physics Institute of Cantabria (IFCA) (RESFI- 2020-3-0028)

Ab initio study of the structural, vibrational, and optical properties of potential parent structures of nitrogen-doped lutetium hydride

The recent report of near-ambient conditions superconductivity in a nitrogen-doped lutetium hydride has inspired a large number of experimental studies with contradictory results. We model from first principles the physical properties of the possible parent structures of the reported superconductors, LuH2 and LuH3. We show that only the phonon band structure of LuH3 can explain the reported Raman spectra due to the presence of hydrogens at the interstitial octahedral sites. However, this structure is stabilized by anharmonicity only above 6 GPa. We find that the intriguing color change with pressure in the reported superconductor is consistent with the optical properties of LuH2, which are determined by the presence of an undamped interband plasmon. The plasmon blueshifts with pressure and modifies the color of the sample without requiring any structural phase transition. Our findings suggest that the main component in the experiments is LuH2 with some extra hydrogen atoms at octahedral sites. Neither LuH2 nor LuH3 superconducts at high temperatures.This work is supported by the European Research Council (ERC) under the European Unions Horizon 2020 research and innovation program (Grant Agreements No. 802533 and No. 946629) and the Department of Education, Universities and Research of the Eusko Jaurlaritza and the University of the Basque Country UPV/EHU (Grant No. IT1527-22). We acknowledge PRACE for awarding us access to Lumi located in CSC's data center in Kajaani, Finland

Anharmonicity Reveals the Tunability of the Charge Density Wave Orders in Monolayer VSe2

VSe2 is a layered compound that has attracted great attention due to its proximity to a ferromagnetic state that is quenched by its charge density wave (CDW) phase. In the monolayer limit, unrelated experiments have reported different CDW orders with different transition temperatures, making this monolayer very controversial. Here we perform first-principles nonperturbative anharmonic phonon calculations in monolayer VSe2 in order to estimate the CDW order and the corresponding transition temperature. They reveal that monolayer VSe2 develops two independent charge density wave orders that compete as a function of strain. Variations of only 1.5% in the lattice parameter are enough to stabilize one order or the other. Moreover, we analyze the impact of external Lennard-Jones interactions, showing that these can act together with anharmonicity to suppress the CDW orders. Our results solve previous experimental contradictions, highlighting the high tunability and substrate dependency of the CDW orders of monolayer VSe2.We acknowledge the computational resources provided by the CESGA and the Aalto Science-IT project. A.O.F. acknowledges the financial support received through the Academy of Finland Project No. 349696. J.D. thanks the Department of Education of the Basque Government for a predoctoral fellowship (Grant No. PRE-2020-1-0220). We thank the Ministry of Science and Education of Spain for financial support through the projects PGC2018-101334-A-C22, GC2018-101334-B-C21, PID2021-122609NB-C22. I.E. acknowledges funding from the Department of Education, Universities and Research of the Eusko Jaurlaritza, and the University of the Basque Country UPV/EHU (Grant No. IT1527-22)

Quantum structural fluxion in superconducting lanthanum polyhydride

The discovery of 250-kelvin superconducting lanthanum polyhydride under high pressure marked a significant advance toward the realization of a room‐temperature superconductor. X-ray diffraction (XRD) studies reveal a nonstoichiometric LaH9.6 or LaH10±δ polyhydride responsible for the superconductivity, which in the literature is commonly treated as LaH10 without accounting for stoichiometric defects. Here, we discover significant nuclear quantum effects (NQE) in this polyhydride, and demonstrate that a minor amount of stoichiometric defects will cause quantum proton diffusion in the otherwise rigid lanthanum lattice in the ground state. The diffusion coefficient reaches ~10−7 cm2/s in LaH9.63 at 150 gigapascals and 240 kelvin, approaching the upper bound value of interstitial hydrides at comparable temperatures. A puzzling phenomenon observed in previous experiments, the positive pressure dependence of the superconducting critical temperature Tc below 150 gigapascals, is explained by a modulation of the electronic structure due to a premature distortion of the hydrogen lattice in this quantum fluxional structure upon decompression, and resulting changes of the electron-phonon coupling. This finding suggests the coexistence of the quantum proton fluxion and hydrogen-induced superconductivity in this lanthanum polyhydride, and leads to an understanding of the structural nature and superconductivity of nonstoichiomectric hydrogen-rich materials.The project is supported by the National Natural Science Foundation of China (Grant No. 11974135, 11874176, 12174170, and 12074138), the Natural Sciences and Engineering Research Council of Canada, the EPSRC through grants EP/P022596/1, and EP/S021981/1, and the startup funds of the office of the Dean of SASN of Rutgers University-Newark. P. T. S. thanks the Department of Materials Science and Metallurgy at the University of Cambridge for generous funding. The work of P. T. S. is further supported through a Trinity Hall research studentship. I. E. acknowledges financial support by the European Research Council (ERC) under the EuropeanUnion’sHorizon 2020 research and innovation program (grant agreement no. 802533)

Switchable chiral transport in charge-ordered kagome metal CsV3Sb5

When electric conductors differ from their mirror image, unusual chiral transport coefficients appear that are forbidden in achiral metals, such as a non-linear electric response known as electronic magnetochiral anisotropy (eMChA)1–6 . Although chiral transport signatures are allowed by symmetry in many conductors without a centre of inversion, they reach appreciable levels only in rare cases in which an exceptionally strong chiral coupling to the itinerant electrons is present. So far, observations of chiral transport have been limited to materials in which the atomic positions strongly break mirror symmetries. Here, we report chiral transport in the centrosymmetric layered kagome metal CsV3Sb5 observed via second-harmonic generation under an in-plane magnetic field. The eMChA signal becomes significant only at temperatures below T′≈ 35 K, deep within the charge-ordered state of CsV 3Sb5 (TCDW ≈ 94 K). This temperature dependence reveals a direct correspondence between electronic chirality, unidirectional charge order7 and spontaneous time-reversal symmetry breaking due to putative orbital loop currents8–10 . We show that the chirality is set by the out-of-plane field component and that a transition from left- to right-handed transport can be induced by changing the field sign. CsV3Sb5 is the first material in which strong chiral transport can be controlled and switched by small magnetic field changes, in stark contrast to structurally chiral materials, which is a prerequisite for applications in chiral electronics.This work was funded by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (MiTopMat, grant agreement no. 715730, and PARATOP, grant agreement no. 757867). This project received funding by the Swiss National Science Foundation (grant no. PP00P2_176789). M.G.V., I.E. and M.G.-A. acknowledge the Spanish Ministerio de Ciencia e Innovacion (grant PID2019-109905GB-C21). M.G.V., C.F. and T.N. acknowledge support from FOR 5249 (QUAST) lead by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation). This work has been supported in part by Basque Government grant IT979-16. This work was also supported by the European Research Council Advanced Grant (no. 742068) ‘TOPMAT’, the Deutsche Forschungsgemeinschaft (Project-ID no. 247310070) ‘SFB 1143’ and the DFG through the Würzburg–Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter ct.qmat (EXC 2147, Project-ID no. 390858490). Open access funding provided by Max Planck Society

Anomalous high-temperature superconductivity in YH6_6

Pressure-stabilized hydrides are a new rapidly growing class of high-temperature superconductors which is believed to be described within the conventional phonon-mediated mechanism of coupling. Here we report the synthesis of yttrium hexahydride Im3m-YH$_6$ that demonstrates the superconducting transition with T$_c$ = 224 K at 166 GPa, much lower than the theoretically predicted (>270 K). The measured upper critical magnetic field B$_c$$_2$(0) of YH$_6$ was found to be 116-158 T, which is 2-2.5 times larger than the calculated value. A pronounced shift of T$_c$ in yttrium deuteride YD$_6$ with the isotope coefficient 0.4 supports the phonon-assisted superconductivity. Current-voltage measurements showed that the critical current I$_c$ and its density J$_c$ may exceed 1.75 A and 3500 A/mm$^2$ at 0 K, respectively, which is comparable with the parameters of commercial superconductors, such as NbTi and YBCO. The superconducting density functional theory (SCDFT) and anharmonic calculations suggest unusually large impact of the Coulomb repulsion in this compound. The results indicate notable departures of the superconducting properties of the discovered YH$_6$ from the conventional Migdal-Eliashberg and Bardeen-Cooper-Schrieffer theories.Comment: arXiv admin note: text overlap with arXiv:1902.1020