A novel all-nitrogen molecular crystal N as a promising high-energy-density material.

All-nitrogen solids, if successfully synthesized, are ideal high-energy-density materials because they store a great amount of energy and produce only harmless N gas upon decomposition. Currently, the only method to obtain all-nitrogen solids is to apply high pressure to N crystals. However, products such as cg-N tend to decompose upon releasing the pressure.

Bubble-wrap carbon: an integration of graphene and fullerenes.

Graphene and fullerene, two types of C allotropes with very different structures and properties, have attracted considerable attention from the scientific community as new forms of carbon for several decades. It will be a great advantage to combine the geometrical features of the two. Herein, we report a series of novel two-dimensional carbon allotropes that possess fullerene-like hollow structures (bubbles) embedded in a graphene sheet.

Reactivity of He with ionic compounds under high pressure.

Until very recently, helium had remained the last naturally occurring element that was known not to form stable solid compounds. Here we propose and demonstrate that there is a general driving force for helium to react with ionic compounds that contain an unequal number of cations and anions. The corresponding reaction products are stabilized not by local chemical bonds but by long-range Coulomb interactions that are significantly modified by the insertion of helium atoms, especially under high pressure.

Honeycomb Boron Allotropes with Dirac Cones: A True Analogue to Graphene.

We propose a series of planar boron allotropes with honeycomb topology and demonstrate that their band structures exhibit Dirac cones at the K point, the same as graphene. In particular, the Dirac point of one honeycomb boron sheet locates precisely on the Fermi level, rendering it as a topologically equivalent material to graphene. Its Fermi velocity (v) is 6.

Quasimolecules in Compressed Lithium.

Under high pressure, some materials form electrides, with valence electrons separated from all atoms and occupying interstitial regions. This is often accompanied by semiconducting or insulating behavior. The interstitial quasiatoms (ISQ) that characterize some high pressure electrides have been postulated to show some of the chemical features of atoms, including the potential of forming covalent bonds.

Macrocycles inserted in graphene: from coordination chemistry on graphene to graphitic carbon oxide.

Tuning electronic structures and properties through chemical modifications has become the focus of recent research on graphene. The adsorption of metal atoms on graphene showed strong potential but is limited due to weak binding. On the other hand, macrocyclic molecules are well known for their strong and selective binding with metal atoms in solutions through coordination bonds.

Anionic chemistry of noble gases: formation of Mg-NG (NG = Xe, Kr, Ar) compounds under pressure.

While often considered to be chemically inert, the reactivity of noble gas elements at elevated pressures is an important aspect of fundamental chemistry. The discovery of Xe oxidation transformed the doctrinal boundary of chemistry by showing that a complete electron shell is not inert to reaction. However, the reductive propensity, i.

Temperature Tunable Self-Doping in Stable Diradicaloid Thin-Film Devices.

FDT and FDT-Br diradicaloids with stable coexisting close-shell and open-shell forms exhibit unconventional self-doping behavior in solid-state electronic devices that is temperature (T) tunable and reversible. The doping is strengthened by the increased T, leading to the absence of off-states (I(off)) in the transistors.

Mercury under Pressure acts as a Transition Metal: Calculated from First Principles.

The inclusion of Hg among the transition metals is readily debated. Recently, molecular HgF4 was synthesized in a low-temperature noble gas but the potential of Hg to form compounds beyond a +2 oxidation state in a stable solid remains unresolved. We propose high-pressure techniques to prepare unusual oxidation states of Hg-based compounds.

Molecular CsF5 and CsF2+.

D5h star-like CsF5 , formally isoelectronic with known XeF5 (-) ion, is computed to be a local minimum on the potential energy surface of CsF5 , surrounded by reasonably large activation energies for its exothermic decomposition to CsF+2 F2 , or to CsF3  (three isomeric forms)+F2 , or for rearrangement to a significantly more stable isomer, a classical Cs(+) complex of F5 (-) . Similarly the CsF2 (+) ion is computed to be metastable in two isomeric forms. In the more symmetrical structures of these molecules there is definite involvement in bonding of the formally core 5p levels of Cs.

High-pressure electrides: the chemical nature of interstitial quasiatoms.

Building on our previous chemical and physical model of high-pressure electrides (HPEs), we explore the effects of interaction of electrons confined in crystals but off the atoms, under conditions of extreme pressure. Electrons in the quantized energy levels of voids or vacancies, interstitial quasiatoms (ISQs), effectively interact with each or with other atoms, in ways that are quite chemical. With the well-characterized Na HPE as an example, we explore the ionic limit, ISQs behaving as anions.

A solid-state effect responsible for an organic quintet state at room temperature and ambient pressure.

A stable organic diradicaloid with an intermolecular quintet at room temperature as a polycrystalline solid is studied. The conclusion is supported by the observation of the ΔMs = ±2 forbidden transition, electron spin resonance (ESR) simulations, and density functional theory (DFT) calculations. In addition, the molecule, as the active component of a device, is an outstanding near-infrared photodetector with detectivity over 10(11) cm Hz(1/2) W(-1) at 1200 nm.

Pressure-stabilized lithium caesides with caesium anions beyond the -1 state.

Main group elements usually assume a typical oxidation state while forming compounds with other species. Group I elements are usually in the +1 state in inorganic materials. Our recent work reveals that pressure may make the inner shell 5p electrons of Cs reactive, causing Cs to expand beyond the +1 oxidation state.

Striking effect of intra- versus intermolecular hydrogen bonding on zwitterions: physical and electronic properties.

We report the synthesis, characterization, and application of novel zwitterions. The zwitterionic structures consist of a positively charged cyanine and negatively charged dienolate moieties, confirmed by experimental observations and theoretical calculations. Single crystal X-ray studies revealed that BIT-(NPh)2 is a coplanar molecule that forms 1-D chains via π-π interactions.

Self-assembled ultrathin nanotubes on diamond (100) surface.

Surfaces of semiconductors are crucially important for electronics, especially when the devices are reduced to the nanoscale. However, surface structures are often elusive, impeding greatly the engineering of devices. Here we develop an efficient method that can automatically explore the surface structures using structure swarm intelligence.

High pressure electrides: a predictive chemical and physical theory.

Electrides, in which electrons occupy interstitial regions in the crystal and behave as anions, appear as new phases for many elements (and compounds) under high pressure. We propose a unified theory of high pressure electrides (HPEs) by treating electrons in the interstitial sites as filling the quantized orbitals of the interstitial space enclosed by the surrounding atom cores, generating what we call an interstitial quasi-atom, ISQ. With increasing pressure, the energies of the valence orbitals of atoms increase more significantly than the ISQ levels, due to repulsion, exclusion by the atom cores, effectively giving the valence electrons less room in which to move.

Two dimensional Dirac carbon allotropes from graphene.

Using a structural search method in combination with first-principles calculations, we found lots of low energy 2D carbon allotropes and examined all possible Dirac points around their Fermi levels. Three amazing 2D Dirac carbon allotropes have been discovered, named as S-graphene, D-graphene and E-graphene. By analyzing the topology correlations among S-, T, net W graphene and graphene, we found that a general rule is valuable for constructing 2D carbon allotropes that are keen to possess Dirac cones in their electronic structures.

Caesium in high oxidation states and as a p-block element.

The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry, rooted in the atomic shell structure. Within compounds, Group I elements, for example, invariably assume the +1 oxidation state, and their chemical properties differ completely from those of the p-block elements. These general rules govern our understanding of chemical structures and reactions.

Trends in the electronic structure of extended gold compounds: implications for use of gold in heterogeneous catalysis.

First-principles electronic structure calculations are presented on a variety of Au compounds and species--encompassing a wide range of formal oxidation states, coordination geometries, and chemical environments--in order to understand the potentially systematic behavior in the nature and energetics of d states that are implicated in catalytic activity. In particular, we monitor the position of the d-band center, which has been suggested to signal catalytic activity for reactions such as CO oxidation. We find a surprising absence of any kind of correlation between the formal oxidation state of Au and the position of the d-band center.

Hybrid functional electronic structure of PbPdO₂, a small-gap semiconductor.

PbPdO₂, a ternary compound containing the lone pair active ion Pb²⁺ and the square planar d⁸Pd²⁺ ion, has attracted recent interest because of the suggestion that its electronic structure, calculated within density functional theory using either the local density or the generalized gradient approximation, displays zero-gap behavior. In light of the potential ease of doping magnetic ions in this structure, it has been suggested that the introduction of spin, in conjunction with zero band gap, can result in unusual magnetic ground states and unusual magnetotransport. It is known that most electronic structure calculations do not properly obtain a band gap even for the simple oxide PdO, and instead obtain a metal or a zero-gap semiconductor.