A novel all-nitrogen molecular crystal N16 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 N2 gas upon decomposition. Currently, the only method to obtain all-nitrogen solids is to apply high pressure to N2 crystals. However, products such as cg-N tend to decompose upon releasing the pressure. Compared to covalent solids, molecular crystals are more likely to remain stable during decompression because they can relax the strain by increasing the intermolecular distances. The challenge of such a route is to find a molecular crystal that can attain a favorable phase under elevated pressure. In this work, we show, by designing a novel N16 molecule (tripentazolylamine) and examining its crystal structures under a series of pressures, that the aromatic units and high molecular symmetry are the key factors to achieving an all-nitrogen molecular crystal. Density functional calculations and structural studies reveal that this new all-nitrogen molecular crystal exhibits a particularly slow enthalpy increase with pressure due to the highly efficient crystal packing of its highly symmetric molecules. Vibration mode calculations and molecular dynamics (MD) simulations show that N16 crystals are metastable at ambient pressure and could remain inactive up to 400 K. The initial reaction steps of the decomposition are calculated by following the pathway of the concerted excision of N2 from the N5 group as revealed by the MD simulations.

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. These carbon allotropes are both thermally and dynamically stable. Calculations using hybrid functionals show that these two-dimensional carbon allotropes could be metals or semiconductors depending on the size and the pattern of the bubbles. The band gap can be as large as 1.66 eV. Due to the unique atomic configuration, some bubble-wrap carbons have unusual negative Poisson's ratios. The combination of graphene and fullerenes provides an appealing approach to design carbon-based materials with dexterous properties. For example, the insertion of the metal atoms inside the bubbles may greatly enhance the functions of such materials in photovoltaics and catalysis.

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. This mechanism also explains the recently discovered reactivity of He and Na under pressure. Our work reveals that helium has the propensity to react with a broad range of ionic compounds at pressures as low as 30 GPa. Since most of the Earth's minerals contain unequal numbers of positively and negatively charged atoms, our work suggests that large quantities of He might be stored in the Earth's lower mantle.

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 (vf) is 6.05 × 105 m/s, close to that of graphene. Although the freestanding honeycomb B allotropes are higher in energy than α-sheet, our calculations show that a metal substrate can greatly stabilize these new allotropes. They are actually more stable than α-sheet sheet on the Ag(111) surface. Furthermore, we find that the honeycomb borons form low-energy nanoribbons that may open gaps or exhibit strong ferromagnetism at the two edges in contrast to the antiferromagnetic coupling of the graphene nanoribbon edges.

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. It is argued that in the observed high-pressure semiconducting Li phase (oC40, Aba2), an example of such quasimolecules is realized. The theoretical evaluation of electron density, electron localization function, Wannier orbitals, and bond indices forms the evidence for covalently bonded ISQ pairs in this material. The quasimolecule concept thus provides a simple chemical perspective on the unusual insulating behavior of such materials, complementing the physical picture previously presented where the global crystal symmetry of the system plays the major role.

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. The alliance of the two substances will largely benefit the two parallel fields: it will provide a scaffold for coordination chemistry as well as a controllable method for tuning the electronic structure of graphene through strong binding with metals. Here, using crown ether as an example, we demonstrate that the embedment of macrocyclic molecules into the graphene honeycomb lattice can be very thermochemically favored. The combination also leads to a family of new materials that has potential in many areas including photolysis and two-dimensional superconductivity.

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.e., gaining electrons and forming anions, has not been proposed or examined for noble gas elements. In this work, we demonstrate, using first-principles electronic structure calculations coupled to an efficient structure prediction method, that Xe, Kr, and Ar can form thermodynamically stable compounds with Mg at high pressure (≥125, ≥250, and ≥250 GPa, respectively). The resulting compounds are metallic and the noble gas atoms are negatively charged, suggesting that chemical species with a completely filled shell can gain electrons, filling their outermost shell(s). Moreover, this work indicates that Mg2NG (NG = Xe, Kr, Ar) are high-pressure electrides with some of the electrons localized at interstitial sites enclosed by the surrounding atoms. Previous predictions showed that such electrides only form in Mg and its compounds at very high pressures (>500 GPa). These calculations also demonstrate strong chemical interactions between the Xe 5d orbitals and the quantized interstitial quasiatom (ISQ) orbitals, including the strong chemical bonding and electron transfer, revealing the chemical nature of the ISQ.

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. Using an advanced structure search algorithm and first-principles electronic structure calculations, we find that under high pressure Hg in Hg-F compounds transfers charge from the d orbitals to the F, thus behaving as a transition metal. Oxidizing Hg to +4 and +3 yielded the thermodynamically stable compounds HgF4 and HgF3. The former consists of HgF4 planar molecules, a typical geometry for d(8) metal centers. HgF3 is metallic and ferromagnetic owing to the d(9) configuration of Hg, with a large gap between its partially occupied and unoccupied bands under high pressure.

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 detailed comparison with known ionic compounds points to high ISQ charge density. ISQs may also form what appear to be covalent bonds with neighboring ISQs or real atoms, similarly confined. Our study looks specifically at quasimolecular model systems (two ISQs, a Li atom and a one-electron ISQ, a Mg atom and two ISQs), in a compression chamber made of He atoms. The electronic density due to the formation of bonding and antibonding molecular orbitals of the compressed entities is recognizable, and a bonding stabilization, which increases with pressure, is estimated. Finally, we use the computed Mg electride to understand metallic bonding in one class of electrides. In general, the space confined between atoms in a high pressure environment offers up quantized states to electrons. These ISQs, even as they lack centering nuclei, in their interactions with each other and neighboring atoms may show anionic, covalent, or metallic bonding, all the chemical features of an atom.

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. Here we predict that pressure can cause large electron transfer from light alkali metals such as Li to Cs, causing Cs to become anionic with a formal charge much beyond -1. Although Li and Cs only form alloys at ambient conditions, we demonstrate that these metals form stable intermetallic LinCs (n=1-5) compounds under pressures higher than 100 GPa. Once formed, these compounds exhibit interesting structural features, including capped cuboids and dimerized icosahedra. Finally, we explore the possibility of superconductivity in metastable LiCs and discuss the effect of the unusual anionic state of Cs on the transition temperature.

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. In contrast, BIT-(NHexyl)2 is a twisted molecule with a dihedral angle of 78° between the charged planes. In charge transport studies, thin films of the flat zwitterion show semiconducting properties, with a hole mobility of 2.1 × 10(-4) cm(2) V(-1) s(-1) while the twisted zwitterion is a high resistivity insulator.

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. Its application to a simple diamond (100) surface reveals an unexpected surface reconstruction featuring self-assembled carbon nanotubes arrays. Such a surface is energetically competitive with the known dimer structure under normal conditions, but it becomes more favourable under a small compressive strain or at high temperatures. The intriguing covalent bonding between neighbouring tubes creates a unique feature of carrier kinetics (that is, one dimensionality of hole states, while two dimensionality of electron states) that could lead to novel design of superior electronics. Our findings highlight that the surface plays vital roles in the fabrication of nanodevices by being a functional part of them.

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. At a high enough pressure, which depends on the element and its orbitals, the frontier atomic electron may become higher in energy than the ISQ, resulting in electron transfer to the interstitial space and the formation of an HPE. By using a He lattice model to compress (with minimal orbital interaction at moderate pressures between the surrounding He and the contained atoms or molecules) atoms and an interstitial space, we are able to semiquantitatively explain and predict the propensity of various elements to form HPEs. The slopes in energy of various orbitals with pressure (s > p > d) are essential for identifying trends across the entire Periodic Table. We predict that the elements forming HPEs under 500 GPa will be Li, Na (both already known to do so), Al, and, near the high end of this pressure range, Mg, Si, Tl, In, and Pb. Ferromagnetic electrides for the heavier alkali metals, suggested by Pickard and Needs, potentially compete with transformation to d-group metals.

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. Based on this rule, we have successfully designed many new 2D carbon allotropes possessing Dirac cones. Their energy order can be well described by an Ising-like model, and some allotropes are energetically more stable than those recently reported. The related electronic structures of these Dirac allotropes are anisotropy distinguished from those of graphene. Moreover, the fact that D- and E-graphene present Dirac cones suggests that sp hybridization or sp(3) hybridization could not suppress the emerging of Dirac features. Our results demonstrate that the Dirac cone and carrier linear dispersion is a very common feature in 2D carbon allotropes and can exist beyond the limitations of fundamental structure features of graphene.

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. Here, first-principles calculations show that, under pressure, caesium atoms can share their 5p electrons to become formally oxidized beyond the +1 state. In the presence of fluorine and under pressure, the formation of CsF(n) (n > 1) compounds containing neutral or ionic molecules is predicted. Their geometry and bonding resemble that of isoelectronic XeF(n) molecules, showing a caesium atom that behaves chemically like a p-block element under these conditions. The calculated stability of the CsF(n) compounds shows that the inner-shell electrons can become the main components of chemical bonds.

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. Instead, we find that the center of the d band displays a nearly linear dependence on the degree of its filling, and this is a general relationship for Au irrespective of the chemistry or geometry of the particular Au compound. Across the compounds examined we find that even small calculated changes in the d-band filling result in a relatively large effect on the position of the d-band center. The results presented here have some important implications for the question of the catalytic activity of Au and indicate that the formal oxidation state is not a determining factor.

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

PbPdO2, a ternary compound containing the lone pair active ion Pb²âº and the square planar d8Pd²âº 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. Here we present density functional calculations employing a screened hybrid functional which correctly obtain a band gap for the electronic structure of PdO. When employed to calculate the electronic ground state of PbPdO2, a band gap is again obtained, which is consistent with both the experimental data on this compound, as well as a consideration of valence states and of metal-oxygen connectivity in the crystal structure. We also present comparisons of the absolute positions (relative to the vacuum level) of the conduction band minima and the valence band maxima in α-PbO, PdO and PbPdO2, which suggest ease of p-type doping in PbPdO2, that has been observed even in nominally pure materials.