Moving beyond traditional 2D materials is now desirable to have switching capabilities (e.g., transistors). Here we propose using graphyne because, as we will show in this letter, obtaining regions of the electronic bandstructure which act as valence and conduction bands, with an apparent bandgap, is found. Here for particular allotropes of graphyne, density of states (DOS) and electronic bandstructure diagrams with E(k) vs k are found for the graphyne allotropes graphyne-1 and graphyne-2 having, respectively, one and two triple C-C carbon-carbon bonds between adjoining benzene rings. The ab initio many-body quantum calculations were performed using both local density approximation (LDA) and generalized gradient approximation (GGA) for density functional theory (DFT).
Using hybrid exchange-correlation functional in ab initio density functional theory calculations, we study magnetic properties and strain effect on the electronic properties of $α$-graphyne monolayer. We find that a spontaneous antiferromagnetic (AF) ordering occurs with energy band gap ($\sim$ 0.5 eV) in the equilibrated $α$-graphyne. Bi-axial tensile strain enhances the stability of AF state as well as the staggered spin moment and value of the energy gap. The antiferromagnetic semiconductor phase is quite robust against moderate carrier filling with threshold carrier density up to 1.7$\time…
Graphdiyne and graphyne are carbon-based two-dimensional (2D) porous atomic lattices, with outstanding physics and excellent application prospects for advanced technologies, like nanoelectronics and energy storage systems. During the last year, B- and N-graphdiyne nanomembranes were experimentally realized. Motivated by the latest experimental advances, in this work we predicted novel N-, B-, P-, Al-, As-, Ga-graphdiyne/graphyne 2D lattices. We then conducted density functional theory simulations to obtain the energy minimized structures and explore the mechanical, thermal stability, electroni…
Seven types of armchair graphyne nanoribbons are investigated with HSE06 functional. The quantum confinements in the graphyne nanoribbons open or increase the band gaps of the corresponding two-dimensional graphynes, which is crucial to high on/off ratio in electronic device operation. The major carrier mobilities of the graphyne nanoribbons with high percentage of sp hybridized carbon atoms are very large. The sparse linking pattern results in small number of frontier crystal orbitals and small deformation potential constants, which are responsible for the large carrier mobilities. Some graph…
The family of graphynes, novel two-dimensional semiconductors with various and fascinating chemical and physical properties, has attracted great interest from both science and industry. Currently, the focus of graphynes is on graphdiyne, or graphyne-2. In this work, we systematically study the effect of acetylene, i.e., carbon-carbon triple bond, links on the electronic and optical properties of a series of graphynes (graphyne-n, where n = 1-5, the number of acetylene bonds) using the ab initio calculations. We find an even-odd pattern, i.e., n = 1, 3, 5 and n = 2, 4 having different features,…
We predict the stabilities of α-graphynes and their boron nitride analogues(α-BNyne), which are considered as competitors of graphene and two-dimensional hexagonal BN. Based on first-principles plane wave method, we investigated the stability and structural transformations of these materials at different sizes using phonon dispersion calculations and ab-initio finite temperature, molecular dynamics simulations. Depending on the number of additional atoms in the edges between the corner atoms of the hexagons, n, both α-graphyne(n) and α-BNyne(n) are stable for even n, but unstable for odd n. α-…
Using density-functional theory and a tight-binding approach we investigate the physical origin of distinct favourable geometries of adsorbed hydrogen atoms in various graphyne structures, and the relation with electronic properties. In particular, H atoms are adsorbed in-plane for $α$-graphyne, and they assume an oblique configuration in all other graphynes, including 6,6,12-graphyne. The origin of different configurations is identified by means of a simple tight-binding model and it is controlled by the tuning of the hopping between sp$^2$-bonded C atoms and sp-bonded C atoms hybridized with…
We study alpha, beta, and gamma graphyne, a class of graphene allotropes with carbon triple bonds, using a first-principles density-functional method and tight-binding calculation. We find that graphyne has versatile Dirac cones and it is due to remarkable roles of the carbon triple bonds in electronic and atomic structures. The carbon triple bonds modulate effective hopping matrix elements and reverse their signs, resulting in Dirac cones with reversed chirality in alpha graphyne, momentum shift of the Dirac point in beta graphyne, and switch of the energy gap in gamma graphyne. Furthermore, …
The modulation of band gap in the two-dimensional carbon materials is of impor- tance for their applications as electronic devices. By first-principles calculations, we propose a model to control the band gap size of γ-graphyne. The model is named as p-n codoping, i. e., using B and N atoms to codope into γ-graphyne. After codoping, B atom plays a role of p doping and N atom acts as n doping. The Fermi energy level returns around the forbidden zone and the band gap of γ-graphyne vary bigger or smaller. Moreover, the gaps exhibit an oscillated behaviour in different codoping configurations. The…
Three new single-atom-thick silicon-carbon stable systems have been found by using of SCED-LCAO and DFT methods. An important position, named bone position, is proposed in these structures. For SiC and Si1C9 system, the bone positions are partially occupied by Si atoms, the plane structure is kept and electronic gap is opened with 0.955 eV and 0.689 eV respectively. For Si2C8 system, the bone positions are fully occupied by Si atoms. It shows a buckled structure with a buckling of 0.05 Å and a Dirac cone at M point. Moreover, the sp hybridization between Si and C atoms in SiC system is found a…
By using of the first-principles calculations based on density functional theory, a novel monolayer planar structure named C64-graphyne is predicted. Tetratomic and hexatomic rings, as well as C-C triple bonds exist in this new stable structure with the lattice parameter of 9.291 Å. The carbon hexatomic ring in C64-graphyne contains two quite distinct C-C bonds, which is known as cyclohexatriene. Its electronic band structures show a semiconductor nature with a narrow direct band gap of 0.35 eV. Interestingly, by substituting one nitrogen atom for a carbon atom in the hexatomic ring or a sp hy…
In this paper we present a detailed computational study of the electronic structure and optical properties of triply-bonded hydrocarbons with linear, and graphyne substructures, with the aim of identifying their potential in opto-electronic device applications. For the purpose, we employed a correlated electron methodology based upon the Pariser-Parr-Pople model Hamiltonian, coupled with the configuration interaction (CI) approach, and studied structures containing up to 42 carbon atoms. Our calculations, based upon large-scale CI expansions, reveal that the linear structures have intense opti…
On the Mechanical, Electronic, and Optical Properties of 8-16-4 Graphyne: A 2D Carbon Allotrope with Dirac Cones
State University of Campinas（坎皮纳斯州立大学）；Center for Computing in Engineering & Sciences, Unicamp（坎皮纳斯州立大学工程与科学计算中心）；University of Brasília（巴西利亚大学）；Federal University of Rio Grande do Norte（北里奥格兰德联邦大学）
We investigate the electronic structure and lattice stability of pristine and functionalized (with either hydrogen or oxygen) $α$-graphyne systems. We identify lattice instabilities due to soft-phonon modes, and describe two mechanisms leading to gap opening in the Dirac-fermion electronic spectrum of these systems: symmetry breaking, connected with the lattice instabilities, and partial incorporation of an $sp^3$-hybrid character in the covalent-bonding network of a buckled hydrogenated $α$-graphyne lattice that retains the symmetries of the parent pristine $α$-graphyne. In the case of an oxy…
A novel two-dimensional carbon allotrope, rectangular graphyne (R-graphyne) with tetra-rings and acetylenic linkages, is proposed by first-principles calculations. Although the bulk R-graphyne exhibits metallic property, the nanoribbons of R-graphyne show distinct electronic structures from the bulk. The most intriguing feature is that band gaps of R-graphene nanoribbons oscillate between semiconductor and metal as a function of width. Particularly, the zigzag edge nanoribbons with half-integer repeating unit cell exhibits unexpected Dirac-like fermions in the band structures. The Dirac-like f…
The electronic and magnetic properties of single 3d transition-metal(TM) atom (V, Cr, Mn, Fe, Co, and Ni) adsorbed graphdiyne (GDY) and graphyne (GY) are systematically studied using first-principles calculations within the density functional framework. We find that the adsorption of TM atom not only efficiently modulates the electronic structures of GDY/GY system, but also introduces excellent magnetic properties, such as half-metal and spin-select half-semiconductor. Such modulation originates from the charge transfer between TM adatom and the GDY/GY sheet as well as the electron redistribut…
Cyclo-Graphyne: A Highly Porous and Semimetallic 2D Carbon Allotrope with Dirac Cones
Federal University of Parana（巴拉那联邦大学）；Interdisciplinary Center for Science, Technology, and Innovation (CICTI), Federal University of Parana（巴拉那联邦大学跨学科科学与技术创新中心）
The presence in the graphyne sheets of a variable amount of sp2/sp1 atoms, which can be transformed into sp3-like atoms by covalent binding with one or two fluorine atoms, respectively, allows one to assume the formation of fulorinated graphynes (fluorographynes) with variable F/C stoichiometry. Here, employing DFT band structure calculations, we examine a series of fluorographynes, and the trends in their stability, structural and electronic properties have been discussed as depending on their stoichiometry: from C2F3 (F/C= 1.5) to C4F7 (F/C= 1.75).
Graphyne nanotubes (GNTs) are nanostructures obtained from rolled up graphyne sheets, in the same way carbon nanotubes (CNTs) are obtained from graphene ones. Graphynes are 2D carbon-allotropes composed of atoms in sp and sp2 hybridized states. Similarly to conventional CNTs, GNTs can present different chiralities and electronic properties. Because of the acetylenic groups (triple bonds), GNTs exhibit large sidewall pores that influence their mechanical properties. In this work, we studied the mechanical response of GNTs under tensile stress using fully atomistic molecular dynamics simulations…
Two-dimensional (2D) carbon materials play an important role in nanomaterials. We propose a new carbon monolayer, named hexagonal-4,4,4-graphyne (H4,4,4-graphyne), which is a nanoporous structure composed of rectangular carbon rings and triple bonds of carbon. Using first-principles calculations, we systematically studied the structure, stability, and band structure of this new material. We found that its energy is much lower than that of some experimental carbon materials and it is stable at least up to 1500 K. In contrast to the single Dirac point band structure of other 2D carbon monolayers…
In this work, we propose a new auxetic (negative Poisson's ratio values) structure, based on a $γ$-graphyne structure, here named $AγG$ $structure$. Graphynes are 2D carbon allotropes with phenylic rings connected by acetylenic groups. The A$γ$G structural/mechanical and electronic properties, as well as its thermal stability, were investigated using classical reactive and quantum molecular dynamics simulations. We found that A$γ$G has a large bandgap of 2.48 eV and is thermally stable at a large range of temperatures. It presents a Young's modulus that is an order of magnitude smaller than th…
Recently, a new carbon-based two-dimensional (2D) material, so called "carbon Ene-yne" (CEY), was successfully synthesized. In this work, we examine electronic, optical and thermal properties of this novel material. We studied the stretchability of CEY via density functional theory (DFT) calculations. Using the PBE and HSE06 functionals, as well as the G$_0$W$_0$ method and the Bethe-Salpeter equation, we systematically explored electronic and optical properties of 2D CEY. In particular, we investigated the change of band-gap and optical properties under uniaxial and biaxial strain. Ab-initio …
Self-assembly and Electronic Properties of Graphyne and Graphdiyne Molecular Wires on Metallic Surfaces
Instituto de Física, Universidade Federal de Uberlândia（联邦乌贝兰迪亚大学物理研究所）；Instituto Federal de Educação, Ciência e Tecnologia do Triângulo Mineiro（米纳斯吉拉斯三角区联邦教育、科学与技术学院）；School of Engineering and Physical Sciences, Keele University（基尔大学工程与物理科学学院）
Carbon has three hybridization forms of sp-, sp2- and sp3-, and the combination of different forms can obtain different kinds of carbon allotropes, such as diamond, carbon nanotubes, fullerene, graphynes (GYs) and graphdiyne (GDY). Among them, the GDY molecule is a single-layer two-dimensional (2D) planar structure material with highly -conjugation formed by sp- and sp2- hybridization. GDY has a carbon atom ring composed of benzene ring and acetylene, which makes GDY have a uniformly distributed pore structure. In addition, GDY planar material have some slight wrinkles, which makes GDY have be…
A graphyne (GY) family composed of the triple (sp) and double (sp2) bonds-hybridized carbon atoms is a promising allotrope of carbon for the development of nanoscale electronic devices. Unlike graphene, the GY family containing carbon sp bonds remains an unsolved problem in efficient two-dimensional (2D) growth due to monomer instability and side reactions. Herein, we synthesize GY into a single 2D layer by chemical vapor deposition (CVD) at low temperatures preventing unexpected reactions, using 1,3,5-tribromo-2,4,6-triethynylbenzene (TBTEB). The CVD-grown GY via a surface-confined coupling b…
Fundamentally new families of carbon single walled nanotubes are proposed. These nanotubes, called graphynes, result from the elongation of covalent interconnections of graphite-based nanotubes by the introduction of yne groups. Similarly to ordinary nanotubes, arm-chair, zig-zag, and chiral graphyne nanotubes are possible. Electronic properties, predicted using tight-binding and ab initio density functional methods, show a rich variety of metallic and semiconducting behaviors.
Holey graphyne (HGY) is a recently synthesized two-dimensional semiconducting allotrope of carbon composed of a regular pattern of six and eight-vertex carbon rings. In this study, based on first-principles density functional theory and molecular dynamics simulations, we predict a similar stable porous boron nitride holey graphyne-like structure that we call BN-holey-graphyne (BN-HGY). The dynamical and thermal stability of the structure at room temperature is confirmed by performing calculations of the phonon dispersion relations, and also ab-initio molecular dynamics simulations. BN-HGY stru…
Ubiquitous graphene is a stricly 2D material representing an ideal adsorbing platform due to its large specific surface area as well as its mechanical strength and resistance to both thermal and chemical stresses. However, graphene as a bulk material has the tendency to form irreversible agglomerates leading to 3D graphitic structures with a significant decrease of the area available for adsorption and no room for gas intercalation. In this paper a novel nanoporous graphite formed by graphtriyne sheets is introduced: its 3D structure is theoretically assessed by means of electronic structure a…
A Concise Review of Recently Synthesized 2D Carbon Allotropes: Amorphous Carbon, Graphynes, Biphenylene and Fullerene Networks
São Paulo State University (UNESP)（圣保罗州立大学）；Universidade Estadual de Campinas (UNICAMP)（坎皮纳斯州立大学）；Federal University of Rio Grande do Norte (UFRN)（北里奥格兰德联邦大学）；University of Brasília (UnB)（巴西利亚大学）；Rice University（莱斯大学）
$α$-graphyne is a two-dimensional sheet of $sp$-$sp^2$ hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, $α$-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable band gap which is attractive for applications. In order to realize applications, it is crucia…
Recently "carbon ene-yne" (CEY), a novel full carbon two-dimensional (2D) material was successfully synthesized by the solvent-phase reaction. Motivated by this experimental effort, we conducted extensive first-principles density functional theory simulations to explore the application prospects of CEY as an anode material for Mg, Na and Li-ion batteries. To simulate the ionic intercalation process in an anode electrode, the adatoms coverage was gradually increased. We then employed Bader charge analysis to evaluate the charge transfer between the adatoms and the CEY nanosheet and finally to r…
Structural, Electronic, and Li-ion Adsorption Properties of PolyPyGY Explored by First-Principles and Machine Learning Simulations: A New Multi-Ringed 2D Carbon Allotrope
The formation energies and electronic structure of europium doped zinc oxide has been determined using DFT and many-body $GW$ methods. In the absence of intrisic defects we find that the europium-$f$ states are located in the ZnO band gap with europium possessing a formal charge of 2+. On the other hand, the presence of intrinsic defects in ZnO allows intraband $f-f$ transitions otherwise forbidden in atomic europium. This result coorroborates with recently observed photoluminescence in the visible red region [1].
Electronic excitations and optical spectra of $CdF_{2}$ are calculated up to ultraviolet employing state-of-the-art techniques based on density functional theory and many-body perturbation theory. The GW scheme proposed by Hedin has been used for the electronic self-energy to calculate single-particle excitation properties as energy bands and densities of states. For optical properties many-body effects, treated within the Bethe-Salpeter equation framework, turn out to be crucial. A bound exciton located about 1 eV below the quasiparticle gap is predicted. Within the present scheme the optical…
We present accurate many-body results of the electronic densities in several solid materials, including Si, NaCl, and Cu. These results are obtained using the ab initio auxiliary-field quantum Monte Carlo (AFQMC) method working in a plane-wave basis with norm-conserving, multiple-projector pseudopotentials. AFQMC has been shown to be an excellent many-body total energy method. Computation of observables and correlation functions other than the ground-state energy requires back-propagation, whose adaption and implementation in the plane-wave basis AFQMC framework are discussed in the present pa…
We present a comprehensive first-principles investigation of the electronic and optical properties of CsK2Sb, a semiconducting material for ultra-bright electron sources for particle accelerators. Our study, based on density-fuctional theory and many-body perturbation theory, provides all the ingredients to model the emission of this material as a photocathode, including band gap, band dispersion, and optical absorption. An accurate description of these properties beyond the mean-field picture is relevant to take into account many-body effects. We discuss our results in the context of state-of…
We present many-body \textit{ab initio} calculations of the electronic and optical properties of semiconducting zigzag carbon nanotubes under uniaxial strain. The GW approach is utilized to obtain the quasiparticle bandgaps and is combined with the Bethe-Salpeter equation to obtain the optical absorption spectrum. We find that the dependence of the electronic bandgaps on strain is more complex than previously predicted based on tight-binding models or density-functional theory. In addition, we show that the exciton energy and exciton binding energy depend significantly on strain, with variatio…
A newly synthesized layered material C2N was investigated based on many- body perturbation theory using GW plus Bethe-Salpeter equation approach. The electronic band gap was determined to be ranging from 3.75 to 1.89 eV from monolayer to bulk. Significant GW quasiparticle corrections, of more than 0.9 eV, to the Kohn-Sham band gaps from the local density approximation (LDA) calculations are found. Strong excitonic effects play a crucial role in optical properties. We found large binding energies of greater than 0.6 eV for bound excitons in few-layer C2N, while it is only 0.04 eV in bulk C2N. A…
Binary alloy phases of the noble metals with main group elements are analyzed in relation to body centered cubic structure with orthorhombic and hexagonal distortions. Stability of these distorted phases is considered on the base of the Fermi sphere - Brillouin zone interaction to understand the important part of the band structure energy contribution to the overall crystal energy. Examination of Brillouin zone - Fermi sphere configurations for several representative phases has shown significance of the electron energy contribution in the formation of distorted structures with superlattices an…
We report computer based simulations of energetics, spectroscopy and electron-phonon interaction of americium using a novel spectral density functional method. This approach gives rise to a new concept of a many-body electronic structure and reveals the unexpected mixed valence regime of Am 5f6 electrons which under pressure acquire the 5f7 valence state. This explains unique properties of Am and addresses the fundamental issue of how the localization delocalization edge is approached from the localized side in a closed shell system.
In this article it will be introduced a new theorem, can be considered a generalization of Hellmann-Feynman theorem[1]. The latter used in conjunction with the quantization of the free energy[2] of a quantum system allows to derive strightly the electronic Heat variations of a quantum electronic system, in its condensed phase of eigenstates, showing its agreement with classical thermodynamics, making then possible to desing ab inito quantum models of the electronic structure in its thermodynamical states.
We develop a theory for the electron-phonon interaction effects on the electronic properties of graphene. We analytically calculate the electron self-energy, spectral function and band velocity renormalization due to phonon-mediated electron-electron interaction. We find that phonon-mediated electron-electron coupling has a large effect on the graphene band structure renormalization, and our analytic theory successfully captures the essential features of the observed graphene electron spectra in the ARPES experiments, predicting a kink at $\sim 200\mathrm{meV}$ below the Fermi level and a redu…
Finite-size (FS) effects are a major source of error in many-body (MB) electronic structure calculations of extended systems. A method is presented to correct for such errors. We show that MB FS effects can be effectively included in a modified local density approximation calculation. A parametrization for the FS exchange-correlation functional is obtained. The method is simple and gives post-processing corrections that can be applied to any MB results. Applications to a model insulator (P$_2$ in a supercell), to semiconducting Si, and to metallic Na show that the method delivers greatly impro…
We present an ab initio $GW$ self-energy calculation of the electronic structure of LaNiO$_2$. With respect to density-functional theory we find that in $GW$ the La 4$f$ states undergo an important $+$2 eV upward shift from the Fermi level, while the O 2$p$ states are pulled down by $-$1.5 eV, thus reinforcing the charge-transfer character of this material. However, $GW$ many-body effects leave the $d$-like bands at the Fermi level almost unaffected, so that the Fermi-surface topology is preserved, unlike in cuprates.
