A Sodium Germanosilicide with Unusual Network Topology.

The germanosilicide NaGeSi (0.4 ≤ ≤ 1.1, 4.

Feasible Route to High-Temperature Ambient-Pressure Hydride Superconductivity.

A key challenge in materials discovery is to find high-temperature superconductors. Hydrogen and hydride materials have long been considered promising materials displaying conventional phonon-mediated superconductivity. However, the high pressures required to stabilize these materials have restricted their application.

Pressure-Induced Amidine Formation via Side-Chain Polymerization in a Charge-Transfer Cocrystal.

Compression of small molecules can induce solid-state reactions that are difficult or impossible under conventional, solution-phase conditions. Of particular interest is the topochemical-like reaction of arenes to produce polymeric nanomaterials. However, high reaction onset pressures and poor selectivity remain significant challenges.

Computational Screening and Stabilization of Boron-Substituted Type-I and Type-II Carbon Clathrates.

Boron substitution represents a promising approach to stabilize carbon clathrate structures, but no thermodynamically stable substitution schemes have been identified for frameworks other than the type-VII (sodalite) structure type. To investigate the possibility for additional tetrahedral carbon-based clathrate networks, more than 5000 unique boron decoration schemes were investigated computationally for type-I and type-II carbon clathrates with a range of guest elements including Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba. Density functional theory calculations were performed at 10 and 50 GPa, and the stability and impact of boron substitution were evaluated.

Synthesis and Post-Processing of Chemically Homogeneous Nanothreads from 2,5-Furandicarboxylic Acid.

Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads-one-dimensional diamondoid polymers formed through the compression of small molecules-represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid.

Conventional High-Temperature Superconductivity in Metallic, Covalently Bonded, Binary-Guest C-B Clathrates.

Inspired by the synthesis of BC ( = Sr, La) compounds in the bipartite sodalite clathrate structure, density functional theory (DFT) calculations are performed on members of this family containing up to two different metal atoms. A DFT-chemical pressure analysis on systems with = Mg, Ca, Sr, Ba reveals that the size of the metal cation, which can be tuned to stabilize the B-C framework, is key for their ambient-pressure dynamic stability. High-throughput density functional theory calculations on 105 3̅ symmetry BC binary-guest compounds (where , are electropositive metal atoms) find 22 that are dynamically stable at 1 atm, expanding the number of potentially synthesizable phases by 19 (18 metals and 1 insulator).

Solid-State Pathway Control via Reaction-Directing Heteroatoms: Ordered Pyridazine Nanothreads through Selective Cycloaddition.

Nanothreads are one-dimensional nanomaterials composed of a primarily sp hydrocarbon backbone, typically formed through the compression of small molecules to high pressures. Although nanothreads have been synthesized from a range of precursors, controlling reaction pathways to produce atomically precise materials remains a difficult challenge. Here, we show how heteroatoms within precursors can serve as "thread-directing" groups by selecting for specific cycloaddition reaction pathways.

Bulk Crystalline 4H-Silicon through a Metastable Allotropic Transition.

We report the synthesis of bulk, highly oriented, crystalline 4H hexagonal silicon (4H-Si), through a metastable phase transformation upon heating the single-crystalline Si_{24} allotrope. Remarkably, the resulting 4H-Si crystallites exhibit an orientation relationship with the Si_{24} crystals, indicating a structural relationship between the two phases. Optical absorption measurements reveal that 4H-Si exhibits an indirect band gap near 1.

Prediction of an Extended Ferroelectric Clathrate.

Using first-principles calculations, we predict a lightweight room-temperature ferroelectric carbon-boron framework in a host-guest clathrate structure. This ferroelectric clathrate, with composition ScB_{3}C_{3}, exhibits high polarization density and low mass density compared with widely used commercial ferroelectrics. Molecular dynamics simulations show spontaneous polarization with a moderate above-room-temperature T_{c} of ∼370  K, which implies large susceptibility and possibly large electrocaloric and piezoelectric constants at room temperature.

Raman studies of hydrogen trapped in AsO·2H at high pressure and low temperature.

Raman spectroscopic measurements of the arsenolite-hydrogen inclusion compound AsO·2H were performed in diamond anvil cells at high pressure and variable temperature down to 80 K. The experimental results were complemented by ab initio molecular dynamics simulations and phonon calculations. Observation of three hydrogen vibrons in AsO·2H is reported in the entire temperature and pressure range studied (up to 24 GPa).

Nanoarchitecture through Strained Molecules: Cubane-Derived Scaffolds and the Smallest Carbon Nanothreads.

Relative to the rich library of small-molecule organics, few examples of ordered extended (i.e., nonmolecular) hydrocarbon networks are known.

Carbon-boron clathrates as a new class of sp-bonded framework materials.

Carbon-based frameworks composed of sp bonding represent a class of extremely lightweight strong materials, but only diamond and a handful of other compounds exist despite numerous predictions. Thus, there remains a large gap between the number of plausible structures predicted and those synthesized. We used a chemical design principle based on boron substitution to predict and synthesize a three-dimensional carbon-boron framework in a host/guest clathrate structure.

Single-crystal synthesis and properties of the open-framework allotrope Si.

Si is a new, open-framework silicon allotrope that is metastable at ambient conditions. Unlike diamond cubic silicon, which is an indirect-gap semiconductor, Si has a quasidirect gap near 1.4 eV, presenting new opportunities for optoelectronic and solar energy conversion devices.

Band Gap Engineering in MASnBr and CsSnBr Perovskites: Mechanistic Insights through the Application of Pressure.

Here we report on the first structural and optical high-pressure investigation of MASnBr (MA = [CHNH]) and CsSnBr halide perovskites. A massive red shift of 0.4 eV for MASnBr and 0.

Evidence for Orientational Order in Nanothreads Derived from Thiophene.

Nanothreads are one-dimensional sp hydrocarbons that pack within pseudohexagonal crystalline lattices. They are believed to lack long-range order along the thread axis and also lack interthread registry. Here we investigate the phase behavior of thiophene up to 35 GPa and establish a pressure-induced phase transition sequence that mirrors previous observations in low-temperature studies.

Phase Transition Pathway Sampling via Swarm Intelligence and Graph Theory.

The prediction of reaction pathways for solid-solid transformations remains a key challenge. Here, we develop a pathway sampling method via swarm intelligence and graph theory and demonstrate that our pallas method is an effective tool to help understand phase transformations in solid-state systems. The method is capable of finding low-energy transition pathways between two minima without having to specify any details of the transition mechanism .

Quantum Dynamics of H_{2} Trapped within Organic Clathrate Cages.

The rotational and translational dynamics of molecular hydrogen trapped within β-hydroquinone clathrate (H_{2}@β-HQ)-a practical example of a quantum particle trapped within an anisotropic confining potential-were investigated using inelastic neutron scattering and Raman spectroscopy. High-resolution vibrational spectra, including those collected from the VISION spectrometer at Oak Ridge National Laboratory, indicate relatively strong attractive interaction between guest and host with a strikingly large splitting of rotational energy levels compared with similar guest-host systems. Unlike related molecular systems in which confined H_{2} exhibits nearly free rotation, the behavior of H_{2}@β-HQ is explained using a two-dimensional (2D) hindered rotor model with barrier height more than 2 times the rotational constant (-16.

Low-energy 3D sp carbons with versatile properties beyond graphite and graphene.

Carbon materials with full sp2-hybridized bonding, e.g. zero-dimensional (0D) fullerenes, 1D carbon nanotubes, and 2D graphene, possess outstanding and unparalleled properties, and have unique scientific and technological importance.

Surprising Stability of Cubane under Extreme Pressure.

The chemical stability of solid cubane under high-pressure was examined with in situ Raman spectroscopy and synchrotron powder X-ray diffraction (PXRD) in a diamond anvil cell (DAC) up to 60 GPa. The Raman modes associated with solid cubane were assigned by comparing experimental data with calculations based on density functional perturbation theory, and low-frequency lattice modes are reported for the first time. The equation of state of solid cubane derived from the PXRD measurements taken during compression gives a bulk modulus of 14.

Chemistry through cocrystals: pressure-induced polymerization of CH·CH to an extended crystalline hydrocarbon.

The 1 : 1 acetylene-benzene cocrystal, CH·CH, was synthesized under pressure in a diamond anvil cell (DAC) and its evolution under pressure was studied with single-crystal X-ray diffraction and Raman spectroscopy. CH·CH is stable up to 30 GPa, nearly 10× the observed polymerization pressure for molecular acetylene to polyacetylene. Upon mild heating at 30 GPa, the cocrystal was observed to undergo an irreversible transition to a mixture of amorphous hydrocarbon and a crystalline phase with similar diffraction to i-carbon, a nanodiamond polymorph currently lacking a definitive structure.

Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp Centers.

Tetracyanomethane, C(CN), is a tetrahedral molecule containing a central sp carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp carbon. High-purity C(CN) was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time.

Zintl Ions within Framework Channels: The Complex Structure and Low-Temperature Transport Properties of NaGe.

Single crystals of a complex Zintl compound with the composition NaGe were synthesized for the first time using a high-pressure/high-temperature approach. Single-crystal diffraction of synchrotron radiation revealed a hexagonal crystal structure with P6/m space group symmetry that is composed of a three-dimensional sp Ge framework punctuated by small and large channels along the crystallographic c axis. Na atoms are inside hexagonal prism-based Ge cages along the small channels, while the larger channels are occupied by layers of disordered sixfold Na rings, which are in turn filled by disordered [Ge] tetrahedra.