Correlated order at the tipping point in the kagome metal CsV3Sb5.

Spontaneously broken symmetries are at the heart of many phenomena of quantum matter and physics more generally. However, determining the exact symmetries that are broken can be challenging due to imperfections such as strain, in particular when multiple electronic orders are competing. This is exemplified by charge order in some kagome systems, where evidence of nematicity and flux order from orbital currents remains inconclusive due to contradictory measurements. Here we clarify this controversy by fabricating highly symmetric samples of a member of this family, CsV3Sb5, and measuring their transport properties. We find that a measurable anisotropy is absent at any temperature in the unperturbed material. However, a pronounced in-plane transport anisotropy appears when either weak magnetic fields or strains are present. A symmetry analysis indicates that a perpendicular magnetic field can indeed lead to in-plane anisotropy by inducing a flux order coexisting with more conventional bond order. Our results provide a unifying picture for the controversial charge order in kagome metals and highlight the need for materials control at the microscopic scale in the identification of broken symmetries.

Chemical Bonding Induces One-Dimensional Physics in Bulk Crystal BiIr4Se8.

One-dimensional (1D) systems persist as some of the most interesting because of the rich physics that emerges from constrained degrees of freedom. A desirable route to harness the properties therein is to grow bulk single crystals of a physically three-dimensional (3D) but electronically 1D compound. Most bulk compounds which approach the electronic 1D limit still field interactions across the other two crystallographic directions and, consequently, deviate from the 1D models. In this paper, we lay out chemical concepts to realize the physics of 1D models in 3D crystals. These are based on both structural and electronic arguments. We present BiIr4Se8, a bulk crystal consisting of linear Bi2+ chains within a scaffolding of IrSe6 octahedra, as a prime example. Through crystal structure analysis, density functional theory calculations, X-ray diffraction, and physical property measurements, we demonstrate the unique 1D electronic configuration in BiIr4Se8. This configuration at ambient temperature is a gapped Su-Schriefer-Heeger system, generated by way of a canonical Peierls distortion involving Bi dimerization that relieves instabilities in a 1D metallic state. At 190 K, an additional 1D charge density wave distortion emerges, which affects the Peierls distortion. The experimental evidence validates our design principles and distinguishes BiIr4Se8 among other quasi-1D bulk compounds. We thus show that it is possible to realize unique electronically 1D materials applying chemical concepts.

Evidence for ground state coherence in a two-dimensional Kondo lattice.

Kondo lattices are ideal testbeds for the exploration of heavy-fermion quantum phases of matter. While our understanding of Kondo lattices has traditionally relied on complex bulk f-electron systems, transition metal dichalcogenide heterobilayers have recently emerged as simple, accessible and tunable 2D Kondo lattice platforms where, however, their ground state remains to be established. Here we present evidence of a coherent ground state in the 1T/1H-TaSe2 heterobilayer by means of scanning tunneling microscopy/spectroscopy at 340 mK. Our measurements reveal the existence of two symmetric electronic resonances around the Fermi energy, a hallmark of coherence in the spin lattice. Spectroscopic imaging locates both resonances at the central Ta atom of the charge density wave of the 1T phase, where the localized magnetic moment is held. Furthermore, the evolution of the electronic structure with the magnetic field reveals a non-linear increase of the energy separation between the electronic resonances. Aided by ab initio and auxiliary-fermion mean-field calculations, we demonstrate that this behavior is inconsistent with a fully screened Kondo lattice, and suggests a ground state with magnetic order mediated by conduction electrons. The manifestation of magnetic coherence in TMD-based 2D Kondo lattices enables the exploration of magnetic quantum criticality, Kondo breakdown transitions and unconventional superconductivity in the strict two-dimensional limit.

Excitonic insulator to superconductor phase transition in ultra-compressed helium.

Helium, the second most abundant element in the universe, exhibits an extremely large electronic band gap of about 20 eV at ambient pressures. While the metallization pressure of helium has been accurately determined, thus far little attention has been paid to the specific mechanisms driving the band-gap closure and electronic properties of this quantum crystal in the terapascal regime (1 TPa = 10 Mbar). Here, we employ density functional theory and many-body perturbation calculations to fill up this knowledge gap. It is found that prior to reaching metallicity helium becomes an excitonic insulator (EI), an exotic state of matter in which electrostatically bound electron-hole pairs may form spontaneously. Furthermore, we predict metallic helium to be a superconductor with a critical temperature of ≈ 20 K just above its metallization pressure and of ≈ 70 K at 100 TPa. These unforeseen phenomena may be critical for improving our fundamental understanding and modeling of celestial bodies.

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±Î´ 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.

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.

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 [Formula: see text] 35 K, deep within the charge-ordered state of CsV3Sb5 (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.

Superconducting hydrides on a quantum landscape.

Reaching superconductivity at ambient conditions is one of the biggest scientific dreams. The discoveries in the last few years at high pressures place hydrogen-based compounds as the best candidates for making it true. As the recent history shows, first-principles calculations are expected to continue guiding the experimental quest in the right track in the coming years. Considering that ionic quantum fluctuations largely affect the crystal structure and the vibrational properties of superconducting hydrides, in many cases making them thermodynamically stable at much lower pressures than expected, it will be crucial to include such effects on the futureab initiopredictions. The prospects for low-pressure high critical-temperature compounds are wide open, even at ambient pressure.

The 2021 room-temperature superconductivity roadmap.

Designing materials with advanced functionalities is the main focus of contemporary solid-state physics and chemistry. Research efforts worldwide are funneled into a few high-end goals, one of the oldest, and most fascinating of which is the search for an ambient temperature superconductor (A-SC). The reason is clear: superconductivity at ambient conditions implies being able to handle, measure and access a single, coherent, macroscopic quantum mechanical state without the limitations associated with cryogenics and pressurization. This would not only open exciting avenues for fundamental research, but also pave the road for a wide range of technological applications, affecting strategic areas such as energy conservation and climate change. In this roadmap we have collected contributions from many of the main actors working on superconductivity, and asked them to share their personal viewpoint on the field. The hope is that this article will serve not only as an instantaneous picture of the status of research, but also as a true roadmap defining the main long-term theoretical and experimental challenges that lie ahead. Interestingly, although the current research in superconductor design is dominated by conventional (phonon-mediated) superconductors, there seems to be a widespread consensus that achieving A-SC may require different pairing mechanisms.In memoriam, to Neil Ashcroft, who inspired us all.

Dominant Role of Quantum Anharmonicity in the Stability and Optical Properties of Infinite Linear Acetylenic Carbon Chains.

Carbyne, an infinite-length straight chain of carbon atoms, is supposed to undergo a second order phase transition from the metallic bond-symmetric cumulene (═C═C═)∞ toward the distorted insulating polyyne chain (-C≡C-)∞ displaying bond-length alternation. However, recent synthesis of ultra long carbon chains (∼6000 atoms, [Nat. Mater., 2016, 15, 634]) did not show any phase transition and detected only the polyyne phase, in agreement with previous experiments on capped finite carbon chains. Here, by performing first-principles calculations, we show that quantum-anharmonicity reduces the energy gain of the polyyne phase with respect to the cumulene one by 71%. The magnitude of the bond-length alternation increases by increasing temperature, in stark contrast with a second order phase transition, confining the cumulene-to-polyyne transition to extremely high and unphysical temperatures. Finally, we predict that a high temperature insulator-to-metal transition occurs in the polyyne phase confined in insulating nanotubes with sufficiently large dielectric constant due to a giant quantum-anharmonic bandgap renormalization.

Strong correlation between electronic bonding network and critical temperature in hydrogen-based superconductors.

By analyzing structural and electronic properties of more than a hundred predicted hydrogen-based superconductors, we determine that the capacity of creating an electronic bonding network between localized units is key to enhance the critical temperature in hydrogen-based superconductors. We define a magnitude named as the networking value, which correlates with the predicted critical temperature better than any other descriptor analyzed thus far. By classifying the studied compounds according to their bonding nature, we observe that such correlation is bonding-type independent, showing a broad scope and generality. Furthermore, combining the networking value with the hydrogen fraction in the system and the hydrogen contribution to the density of states at the Fermi level, we can predict the critical temperature of hydrogen-based compounds with an accuracy of about 60 K. Such correlation is useful to screen new superconducting compounds and offers a deeper understating of the chemical and physical properties of hydrogen-based superconductors, while setting clear paths for chemically engineering their critical temperatures.

The stochastic self-consistent harmonic approximation: calculating vibrational properties of materials with full quantum and anharmonic effects.

The efficient and accurate calculation of how ionic quantum and thermal fluctuations impact the free energy of a crystal, its atomic structure, and phonon spectrum is one of the main challenges of solid state physics, especially when strong anharmonicy invalidates any perturbative approach. To tackle this problem, we present the implementation on a modular Python code of the stochastic self-consistent harmonic approximation (SSCHA) method. This technique rigorously describes the full thermodynamics of crystals accounting for nuclear quantum and thermal anharmonic fluctuations. The approach requires the evaluation of the Born-Oppenheimer energy, as well as its derivatives with respect to ionic positions (forces) and cell parameters (stress tensor) in supercells, which can be provided, for instance, by first principles density-functional-theory codes. The method performs crystal geometry relaxation on the quantum free energy landscape, optimizing the free energy with respect to all degrees of freedom of the crystal structure. It can be used to determine the phase diagram of any crystal at finite temperature. It enables the calculation of phase boundaries for both first-order and second-order phase transitions from the Hessian of the free energy. Finally, the code can also compute the anharmonic phonon spectra, including the phonon linewidths, as well as phonon spectral functions. We review the theoretical framework of the SSCHA and its dynamical extension, making particular emphasis on the physical inter pretation of the variables present in the theory that can enlighten the comparison with any other anharmonic theory. A modular and flexible Python environment is used for the implementation, which allows for a clean interaction with other packages. We briefly present a toy-model calculation to illustrate the potential of the code. Several applications of the method in superconducting hydrides, charge-density-wave materials, and thermoelectric compounds are also reviewed.

Anomalous High-Temperature Superconductivity in YH6.

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, the synthesis of one of the best-known high-TC superconductors-yttrium hexahydride I m 3 ¯ m -YH6 is reported, which displays a superconducting transition at ≈224 K at 166 GPa. The extrapolated upper critical magnetic field Bc2 (0) of YH6 is surprisingly high: 116-158 T, which is 2-2.5 times larger than the calculated value. A pronounced shift of TC in yttrium deuteride YD6 with the isotope coefficient 0.4 supports the phonon-assisted superconductivity. Current-voltage measurements show that the critical current IC and its density JC may exceed 1.75 A and 3500 A mm-2 at 4 K, respectively, which is higher than that of the commercial superconductors, such as NbTi and YBCO. The results of superconducting density functional theory (SCDFT) and anharmonic calculations, together with anomalously high critical magnetic field, suggest notable departures of the superconducting properties from the conventional Migdal-Eliashberg and Bardeen-Cooper-Schrieffer theories, and presence of an additional mechanism of superconductivity.

van der Waals driven anharmonic melting of the 3D charge density wave in VSe2.

Understanding of charge-density wave (CDW) phases is a main challenge in condensed matter due to their presence in high-Tc superconductors or transition metal dichalcogenides (TMDs). Among TMDs, the origin of the CDW in VSe2 remains highly debated. Here, by means of inelastic x-ray scattering and first-principles calculations, we show that the CDW transition is driven by the collapse at 110 K of an acoustic mode at qCDW = (2.25 0 0.7) r.l.u. The softening starts below 225 K and expands over a wide region of the Brillouin zone, identifying the electron-phonon interaction as the driving force of the CDW. This is supported by our calculations that determine a large momentum-dependence of the electron-phonon matrix-elements that peak at the CDW wave vector. Our first-principles anharmonic calculations reproduce the temperature dependence of the soft mode and the TCDW onset only when considering the out-of-plane van der Waals interactions, which reveal crucial for the melting of the CDW phase.

Nanoscale-Confined Terahertz Polaritons in a van der Waals Crystal.

Electromagnetic field confinement is crucial for nanophotonic technologies, since it allows for enhancing light-matter interactions, thus enabling light manipulation in deep sub-wavelength scales. In the terahertz (THz) spectral range, radiation confinement is conventionally achieved with specially designed metallic structures-such as antennas or nanoslits-with large footprints due to the rather long wavelengths of THz radiation. In this context, phonon polaritons-light coupled to lattice vibrations-in van der Waals (vdW) crystals have emerged as a promising solution for controlling light beyond the diffraction limit, as they feature extreme field confinements and low optical losses. However, experimental demonstration of nanoscale-confined phonon polaritons at THz frequencies has so far remained elusive. Here, it is provided by employing scattering-type scanning near-field optical microscopy combined with a free-electron laser to reveal a range of low-loss polaritonic excitations at frequencies from 8 to 12 THz in the vdW semiconductor α-MoO3 . In this study, THz polaritons are visualized with: i) in-plane hyperbolic dispersion, ii) extreme nanoscale field confinement (below λo  /75), and iii) long polariton lifetimes, with a lower limit of >2 ps.

Weak Dimensionality Dependence and Dominant Role of Ionic Fluctuations in the Charge-Density-Wave Transition of NbSe_{2}.

Contradictory experiments have been reported about the dimensionality effect on the charge-density-wave transition in 2H NbSe_{2}. While scanning tunneling experiments on single layers grown by molecular beam epitaxy measure a charge-density-wave transition temperature in the monolayer similar to the bulk, around 33 K, Raman experiments on exfoliated samples observe a large enhancement of the transition temperature up to 145 K. By employing a nonperturbative approach to deal with anharmonicity, we calculate from first principles the temperature dependence of the phonon spectra both for bulk and monolayer. In both cases, the charge-density-wave transition temperature is estimated as the temperature at which the phonon energy of the mode driving the structural instability vanishes. The obtained transition temperature in the bulk is around 59 K, in rather good agreement with experiments, and it is just slightly increased in the single-layer limit to 73 K, showing the weak dependence of the transition on dimensionality. Environmental factors could motivate the disagreement between the transition temperatures reported by experiments. Our analysis also demonstrates the predominance of ionic fluctuations over electronic ones in the melting of the charge-density-wave order.

Infrared Permittivity of the Biaxial van der Waals Semiconductor α-MoO3 from Near- and Far-Field Correlative Studies.

The biaxial van der Waals semiconductor α-phase molybdenum trioxide (α-MoO3 ) has recently received significant attention due to its ability to support highly anisotropic phonon polaritons (PhPs)-infrared (IR) light coupled to lattice vibrations-offering an unprecedented platform for controlling the flow of energy at the nanoscale. However, to fully exploit the extraordinary IR response of this material, an accurate dielectric function is required. Here, the accurate IR dielectric function of α-MoO3 is reported by modeling far-field polarized IR reflectance spectra acquired on a single thick flake of this material. Unique to this work, the far-field model is refined by contrasting the experimental dispersion and damping of PhPs, revealed by polariton interferometry using scattering-type scanning near-field optical microscopy (s-SNOM) on thin flakes of α-MoO3 , with analytical and transfer-matrix calculations, as well as full-wave simulations. Through these correlative efforts, exceptional quantitative agreement is attained to both far- and near-field properties for multiple flakes, thus providing strong verification of the accuracy of this model, while offering a novel approach to extracting dielectric functions of nanomaterials. In addition, by employing density functional theory (DFT), insights into the various vibrational states dictating the dielectric function model and the intriguing optical properties of α-MoO3 are provided.

Anharmonicity and Doping Melt the Charge Density Wave in Single-Layer TiSe2.

Low-dimensional systems with a vanishing band gap and a large electron-hole interaction have been proposed to be unstable toward exciton formation. As the exciton binding energy increases in low dimension, conventional wisdom suggests that excitonic insulators should be more stable in 2D than in 3D. Here we study the effects of the electron-hole interaction and anharmonicity in single-layer TiSe2. We find that, contrary to the bulk case and to the generally accepted picture, in single-layer TiSe2, the electron-hole exchange interaction is much smaller in 2D than in 3D and it has weak effects on phonon spectra. By calculating anharmonic phonon spectra within the stochastic self-consistent harmonic approximation, we obtain TCDW ≈ 440 K for an isolated and undoped single layer and TCDW ≈ 364 K for an electron-doping n = 4.6 × 1013 cm-2, close to the experimental result of 200-280 K on supported samples. Our work demonstrates that anharmonicity and doping melt the charge density wave in single-layer TiSe2.

Broad spectral tuning of ultra-low-loss polaritons in a van der Waals crystal by intercalation.

Phonon polaritons-light coupled to lattice vibrations-in polar van der Waals crystals are promising candidates for controlling the flow of energy on the nanoscale due to their strong field confinement, anisotropic propagation and ultra-long lifetime in the picosecond range1-5. However, the lack of tunability of their narrow and material-specific spectral range-the Reststrahlen band-severely limits their technological implementation. Here, we demonstrate that intercalation of Na atoms in the van der Waals semiconductor α-V2O5 enables a broad spectral shift of Reststrahlen bands, and that the phonon polaritons excited show ultra-low losses (lifetime of 4 ± 1 ps), similar to phonon polaritons in a non-intercalated crystal (lifetime of 6 ± 1 ps). We expect our intercalation method to be applicable to other van der Waals crystals, opening the door for the use of phonon polaritons in broad spectral bands in the mid-infrared domain.

Quantum crystal structure in the 250-kelvin superconducting lanthanum hydride.

The discovery of superconductivity at 200 kelvin in the hydrogen sulfide system at high pressures1 demonstrated the potential of hydrogen-rich materials as high-temperature superconductors. Recent theoretical predictions of rare-earth hydrides with hydrogen cages2,3 and the subsequent synthesis of LaH10 with a superconducting critical temperature (Tc) of 250 kelvin4,5 have placed these materials on the verge of achieving the long-standing goal of room-temperature superconductivity. Electrical and X-ray diffraction measurements have revealed a weakly pressure-dependent Tc for LaH10 between 137 and 218 gigapascals in a structure that has a face-centred cubic arrangement of lanthanum atoms5. Here we show that quantum atomic fluctuations stabilize a highly symmetrical [Formula: see text] crystal structure over this pressure range. The structure is consistent with experimental findings and has a very large electron-phonon coupling constant of 3.5. Although ab initio classical calculations predict that this [Formula: see text] structure undergoes distortion at pressures below 230 gigapascals2,3, yielding a complex energy landscape, the inclusion of quantum effects suggests that it is the true ground-state structure. The agreement between the calculated and experimental Tc values further indicates that this phase is responsible for the superconductivity observed at 250 kelvin. The relevance of quantum fluctuations calls into question many of the crystal structure predictions that have been made for hydrides within a classical approach and that currently guide the experimental quest for room-temperature superconductivity6-8. Furthermore, we find that quantum effects are crucial for the stabilization of solids with high electron-phonon coupling constants that could otherwise be destabilized by the large electron-phonon interaction9, thus reducing the pressures required for their synthesis.