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Diamond possesses exceptional physical properties due to its remarkably strong carbon-carbon bonding, leading to significant resilience to structural transformations at very high pressures and temperatures. Despite several experimental attempts, synthesis and recovery of the theoretically predicted post-diamond BC8 phase remains elusive. Through quantum accurate, multi-million atom molecular dynamics (MD) simulations, we have uncovered the extreme metastability of diamond at very high pressures, significantly exceeding its range of thermodynamic stability. We predict the post-diamond BC8 phase to be experimentally accessible only within a narrow high pressure-temperature region of the carbon phase diagram. The diamond to BC8 transformation proceeds through pre-melting followed by BC8 nucleation and growth in the metastable carbon liquid. We propose a double-shock compression pathway to achieve BC8 synthesis, which is currently being explored in theory-inspired experiments at the National Ignition Facility.

Carbon at extreme conditions is the focus of intensive scientific inquiry due to its importance for applications in inertial confinement fusion experiments and for understanding the interior structure of carbon-rich exoplanets. The extreme metastability of diamond at very high pressures has been discovered in recent dynamic compression experiments. This work addresses an important question about the existence of other competitive metastable carbon phases that might be observed in shock experiments. It was found that diamond polytypes, carbon crystals with mixed cubic and hexagonal diamond stacking planes, are the only metastable carbon crystal phases energetically competitive with cubic diamond at pressures between 100 and 1,000 GPa. Above 1 TPa, no metastable phases are found to be energetically competitive with thermodynamically stable BC8 and simple cubic phases. The existence of low enthalpy diamond polytypes suggests that they are likely candidates for metastable phases of carbon to appear upon shockwave loading of diamond.

A Spectral Neighbor Analysis (SNAP) machine learning interatomic potential (MLIP) has been developed for simulations of carbon at extreme pressures (up to 5 TPa) and temperatures (up to 20,000 K). This was achieved using a large database of experimentally relevant quantum molecular dynamics (QMD) data, training the SNAP potential using a robust machine learning methodology, and performing extensive validation against QMD and experimental data. The resultant carbon MLIP demonstrates unprecedented accuracy and transferability in predicting the carbon phase diagram, melting curves of crystalline phases, and the shock Hugoniot, all within 3% of QMD. By achieving quantum accuracy and efficient implementation on leadership class high performance computing systems, SNAP advances frontiers of classical MD simulations by enabling atomic-scale insights at experimental time and length scales.

Silver pentazolate, a high energy density compound containing cyclo-N5- anion, has recently been synthesized at ambient conditions. However, due to high sensitivity to irradiation, its crystal structure has not been determined. In this work, silver-nitrogen crystalline compounds at ambient conditions and high pressures, up to 100 GPa, are predicted and characterized by performing first-principles evolutionary crystal structure searching with variable stoichiometry. It is found that newly discovered AgN5 and AgN6 are the only thermodynamically stable silver-nitrogen compounds at pressures between 42 and 80 GPa. In contrast to AgN5, pentazolate AgN6 compound contains N2 diatomic molecules in addition to cyclo-N5-. These AgN5 and AgN6 crystals are metastable at ambient conditions with positive formation enthalpies of 54.95 kJ/mol and 46.24 kJ/mol, respectively. The underlying cause of the stability of cyclo-N5- silver pentazolates is the enhanced aromaticity enabled by the charge transfer from silver atoms to nitrogen rings. To aid in experimental identification of these materials, calculated Raman spectra are reported at ambient pressure: the frequencies of N5- vibrational modes of AgN5 are in good agreement with those measured in experiment.

The electronic and magnetic properties of transition metal dichalcogenides are known to be extremely sensitive to their structure. In this paper we study the effect of structure on the electronic and magnetic properties of mono- and bilayer $VSe_2$ films grown using molecular beam epitaxy. $VSe_2$ has recently attracted much attention due to reports of emergent ferromagnetism in the 2D limit. To understand this important compound, high quality 1T and distorted 1T films were grown at temperatures of 200 $^\text{o}$C and 450 $^\text{o}$C respectively and studied using 4K Scanning Tunneling Microscopy/Spectroscopy. The measured density of states and the charge density wave (CDW) patterns were compared to band structure and phonon dispersion calculations. Films in the 1T phase reveal different CDW patterns in the first layer compared to the second. Interestingly, we find the second layer of the 1T-film shows a CDW pattern with 4a $\times$ 4a periodicity which is the 2D version of the bulk CDW observed in this compound. Our phonon dispersion calculations confirm the presence of a soft phonon at the correct wavevector that leads to this CDW. In contrast, the first layer of distorted 1T phase films shows a strong stripe feature with varying periodicities, while the second layer displays no observable CDW pattern. Finally, we find that the monolayer 1T $VSe_2$ film is weakly ferromagnetic, with ~ $3.5 {\mu}_B$ per unit similar to previous reports., Comment: 19 pages, 10 figures

Polynitrogen compounds have attracted great interest due to their potential applications as high energy density materials. Most recently, a rich variety of alkali polynitrogens (R_{x}N_{y}; R=Li, Na, and Cs) have been predicted to be stable at high pressures and one of them, CsN_{5} has been recently synthesized. In this work, various potassium polynitrides are investigated using first-principles crystal structure search methods. Several novel molecular crystals consisting of N_{4} chains, N_{5} rings, and N_{6} rings stable at high pressures are discovered. In addition, an unusual nitrogen-rich metallic crystal with stoichiometry K_{2}N_{16} consisting of a planar two-dimensional extended network of nitrogen atoms arranged in fused eighteen atom rings is found to be stable above 70 GPa. An appreciable electron transfer from K to N atoms is responsible for the appearance of unexpected chemical bonding in these crystals. The thermodynamic stability and high pressure phase diagram is constructed. The electronic and vibrational properties of the layered polynitrogen K_{2}N_{16} compound are investigated, and the pressure-dependent IR-spectrum is obtained to assist in experimental discovery of this new high-nitrogen content material.

Ternary C_{x}N_{y}O_{z} compounds are actively researched as novel high energy density and ultrahard materials. Although some synthesis work has been performed at ambient conditions, very little is known about the high pressure chemistry of of C_{x}N_{y}O_{z} compounds. In this work, first principles variable-composition evolutionary structure prediction calculations are performed with the goal of discovering novel mixed C_{x}N_{y}O_{z} materials at ambient and high pressure conditions. By systematically searching ternary variable composition crystalline materials, the full ternary phase diagram is constructed in the range of pressures from 0 to 100 GPa. The search finds the C_{2}N_{2}O crystal containing extended covalent network of C, N, and O atoms, having space group symmetry Cmc2_{1}, and stable above just 10 GPa. Several other novel metastable (CO)_{x}-(N)_{y} crystalline compounds discovered during the search, including two polymorphs of C_{2}NO_{2} and two polymorphs of C_{3}N_{2}O_{3} crystals are found to be energetically favorable compared to polymeric carbon monoxide (CO) and nitrogen. Predicted new compounds are characterized by their Raman spectra and equations of state.

Tin sulfides SnxSy are important class of materials that are actively investigated as novel photovoltaic and water splitting materials. First-principles evolutionary crystal structure search is performed with the goal of constructing the complete phase diagram of SnxSy and discover new phases as well as new compounds of varying stoichiometry at ambient conditions and pressures up to 100 GPa. The ambient phase of SnS2 with P3m1 symmetry remains stable up to 30 GPa. Another ambient phase, SnS experiences a series of phase transformations: including \alpha-SnS to \beta-SnS at 9 GPa, followed by \beta-SnS to \gamma-SnS at 40 GPa. \gamma-SnS is a new high-pressure metallic phase with Pm3m space group symmetry stable up to 100 GPa, which becomes a superconductor with a maximum Tc= 9.6 K at 40 GPa. Another new metallic compound, Sn3S4 with I43d space group symmetry, is predicted to be stable at pressures above 15 GPa, which also becomes a superconductor with a maximum Tc=21.8 K at 30 GPa.

SnxSey crystalline compounds consisting of Sn and Se atoms of varying composition are systematically investigated at pressures from 0 to 100 GPa using the first-principles evolutionary crystal structure search method based on density functional theory (DFT). All known experimental phases of SnSe and SnSe2 are found without any prior input. A second order polymorphic phase transition from SnSe-Pnma phase to SnSe-Cmcm phase is predicted at 2.5 GPa. Initially being semiconducting, this phase becomes metallic at 7.3 GPa. Upon further increase of pressure up to 36.6 GPa, SnSe-Cmcm phase is transformed to CsCl-type SnSe-Pm3m phase, which remains stable at even higher pressures. A metallic compound with different stoichiometry, Sn3Se4-I43d, is found to be thermodynamically stable from 18 GPa to 70 GPa. Known semiconductor tin diselenide SnSe2-P3m1 phase is found to be thermodynamically stable from ambient pressure up to 18 GPa. Initially being semiconducting, it experiences metalization at pressures above 8 GPa.

Two new crystalline compounds, pentazole (N_{5}H) and ammonium pentazolate (NH_{4})(N_{5}), both featuring cyclo-{\rm N_{5}^{-}} are discovered using first principles evolutionary search of the nitrogen-rich portion of the hydro-nitrogen binary phase diagram (N_{x}H_{y}, x\geqy) at high pressures. Both crystals consist of the pentazolate N_{5}^{-} anion and ammonium NH_{4}^{+} or hydrogen H^{+} cations. These two crystals are predicted to be thermodynamically stable at pressures above 30 GPa for (NH_{4})(N_{5}) and 50 GPa for pentazole N_{5}H. The chemical transformation of ammonium azide (NH_{4})(N_{3}) mixed with di-nitrogen (N_{2}) to ammonium pentazolate (NH_{4})(N_{5}) is predicted to become energetically favorable above 12.5 GPa. To assist in identification of newly synthesized compounds in future experiments, the Raman spectra of both crystals are calculated and mode assignments are made as a function of pressure up to 75 GPa.

The pentazolates, the last all-nitrogen members of the azole series, have been notoriously elusive for the last hundred years despite enormous efforts to make these compounds in either gas or condensed phases. Here we report a successful synthesis of a solid state compound consisting of isolated pentazolate anions N5-, which is achieved by compressing and laser heating cesium azide (CsN3) mixed with N2 cryogenic liquid in a diamond anvil cell. The experiment was guided by theory, which predicted the transformation of the mixture at high pressures to a new compound, cesium pentazolate salt (CsN5). Electron transfer from Cs atoms to N5 rings enables both aromaticity in the pentazolates as well as ionic bonding in the CsN5 crystal. This work provides a critical insight into the role of extreme conditions in exploring unusual bonding routes that ultimately lead to the formation of novel high nitrogen content species.

The layer dependent structural, electronic and vibrational properties of SnS2 and SnSe2 are investigated using first-principles density functional theory (DFT). The in-plane lattice constants, interlayer distances and binding energies are found to be layer-independent. Bulk SnS2 and SnSe2 are both indirect band gap semiconductors with Eg = 2.18 eV and 1.07 eV, respectively. Few-layer and monolayer 2D systems also possess an indirect band gap, which is increased to 2.41 eV and 1.69 eV for single layers of SnS2 and SnSe2. The effective mass theory of 2D excitons, which takes into account the combined effect of the anisotropy, non-local 2D screening and layer-dependent 3D screening, predicts strong excitonic effects. The binding energy of indirect excitons in monolayer samples, Ex~0.9 eV, is substantially reduced to Ex = 0.14 eV in bulk SnS2 and Ex = 0.09 eV in bulk SnSe2. The layer-dependent Raman spectra display a strong decrease of intensities of the Raman active A1g mode upon decreasing the number of layers down to a monolayer, by a factor of 7 in the case of SnS2 and a factor of 20 in the case of SnSe2 which can be used to identify number of layers in a 2D sample.

Sodium pentazolates NaN5 andNa2N5, new high energy density materials, are discovered during first principles crystal structure search for the compounds of varying amounts of elemental sodium and nitrogen. The pentazole anion N5- is stabilized in the condensed phase by sodium Na+ cations at pressures exceeding 20 GPa, and becomes metastable upon release of pressure. The sodium azide (NaN3) precursor is predicted to undergo a chemical transformation above 50 GPa into sodium pentazolates NaN5 and Na2N5. The calculated Raman spectrum of NaN5 is in agreement with the experimental Raman spectrum of a previously unidentified substance appearing upon compression and heating of NaN3.