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Large-scale atomistic molecular dynamics (MD) simulations provide an exceptional opportunity to advance the fundamental understanding of carbon under extreme conditions of high pressures and temperatures. However, the fidelity of these simulations depends heavily on the accuracy of classical interatomic potentials governing the dynamics of many-atom systems. This study critically assesses several popular empirical potentials for carbon, as well as machine learning interatomic potentials (MLIPs), in their ability to simulate a range of physical properties at high pressures and temperatures, including the diamond equation of state, its melting line, shock Hugoniot, uniaxial compressions, and the structure of liquid carbon. Empirical potentials fail to accurately predict the behavior of carbon under high pressure-temperature conditions. In contrast, MLIPs demonstrate quantum accuracy, with Spectral Neighbor Analysis Potential (SNAP) and atomic cluster expansion (ACE) being the most accurate in reproducing the density functional theory results. ACE displays remarkable transferability despite not being specifically trained for extreme conditions. Furthermore, ACE and SNAP exhibit superior computational performance on graphics processing unit-based systems in billion atom MD simulations, with SNAP emerging as the fastest. In addition to offering practical guidance in selecting an interatomic potential with a fine balance of accuracy, transferability, and computational efficiency, this work also highlights transformative opportunities for groundbreaking scientific discoveries facilitated by quantum-accurate MD simulations with MLIPs on emerging exascale supercomputers., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

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 multimillion 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 premelting followed by BC8 nucleation and growth in the metastable carbon liquid. We propose a double-shock compression pathway for BC8 synthesis, which is currently being explored in experiments at the National Ignition Facility.

Silver pentazolate, a high energy density compound containing the cyclo-N 5 - anion, has recently been synthesized under ambient conditions. However, due to high sensitivity to irradiation, its crystal structure has not been determined. In this work, silver-nitrogen crystalline compounds under ambient conditions and at 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 AgN 5 and AgN 6 are the only thermodynamically stable silver-nitrogen compounds at pressures between 42 and 80 GPa. In contrast to AgN 5 , the pentazolate AgN 6 compound contains N 2 diatomic molecules in addition to cyclo-N 5 - . These AgN 5 and AgN 6 crystals are metastable under ambient conditions with positive formation enthalpies of 54.95 kJ mol -1 and 46.24 kJ mol -1 , respectively. The underlying cause of the stability of cyclo-N 5 - silver pentazolates is the enhanced aromaticity enabled by the charge transfer from silver atoms to nitrogen rings. To aid in the experimental identification of these materials, calculated Raman spectra are reported at ambient pressure: the frequencies of N 5 - vibrational modes of AgN 5 are in good agreement with those measured in the experiment.

Charge mobility of crystalline organic semiconductors (OSC) is limited by local dynamic disorder. Recently, the charge mobility for several high mobility OSCs, including TIPS-pentacene, were accurately predicted from a density functional theory (DFT) simulation constrained by the crystal structure and the inelastic neutron scattering spectrum, which provide direct measures of the structure and the dynamic disorder in the length scale and energy range of interest. However, the computational expense required for calculating all of the atomic and molecular forces is prohibitive. Here we demonstrate the use of density functional tight binding (DFTB), a semiempirical quantum mechanical method that is 2 to 3 orders of magnitude more efficient than DFT. We show that force matching a many-body interaction potential to DFT derived forces yields highly accurate DFTB models capable of reproducing the low-frequency intricacies of experimental inelastic neutron scattering (INS) spectra and accurately predicting charge mobility. We subsequently predicted charge mobilities from our DFTB model of a number of previously unstudied structural analogues to TIPS-pentacene using dynamic disorder from DFTB and transient localization theory. The approach we establish here could provide a truly rapid simulation pathway for accurate materials properties prediction, in our vision applied to new OSCs with tailored properties.

Interlayer interactions in layered transition metal dichalcogenides are known to be important for describing their electronic properties. Here, we demonstrate that the absence of interlayer coupling in monolayer VTe 2 also causes their structural modification from a distorted 1T' structure in bulk and multilayer samples to a hexagonal 1T structure in the monolayer. X-ray photoemission spectroscopy indicates that this structural transition is associated with electron transfer from the vanadium d bands to the tellurium atoms for the monolayer. This charge transfer may reduce the in-plane d orbital hybridization and thus favor the undistorted 1T structure. Phonon-dispersion calculations show that, in contrast to the 1T' structure, the 1T structure exhibits imaginary phonon modes that lead to a charge density wave (CDW) instability, which is also observed by low-temperature scanning tunneling microscopy as a 4 × 4 periodic lattice distortion. Thus, this work demonstrates a novel CDW material, whose properties are tuned by interlayer interactions.

Tin sulfides, Sn x S y , are an important class of materials that are actively investigated as novel photovoltaic and water splitting materials. A first-principles evolutionary crystal structure search is performed with the goal of constructing the complete phase diagram of Sn x S y and discovering new phases as well as new compounds of varying stoichiometry at ambient conditions and pressures up to 100 GPa. The ambient phase of SnS 2 with P 3 ¯ m 1 symmetry remains stable up to 28 GPa. Another ambient phase, SnS, experiences a series of phase transformations including α -SnS to β -SnS at 9 GPa, followed by β -SnS to γ -SnS at 40 GPa. γ -SnS is a new high-pressure metallic phase with P m 3 ¯ m space group symmetry stable up to 100 GPa, which becomes a superconductor with a maximum T c = 9.74 K at 40 GPa. Another new metallic compound, Sn 3 S 4 with I 4 ¯ 3 d space group symmetry, is predicted to be stable at pressures above 15 GPa, which also becomes a superconductor with relatively high T c = 21.9 K at 30 GPa.