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One of the most common and important destructive attacks on the victim system is Advanced Persistent Threat (APT)-attack. The APT attacker can achieve his hostile goals by obtaining information and gaining financial benefits regarding the infrastructure of a network. One of the solutions to detect a secret APT attack is using network traffic. Due to the nature of the APT attack in terms of being on the network for a long time and the fact that the network may crash because of high traffic, it is difficult to detect this type of attack. Hence, in this study, machine learning methods such as C5.0 decision tree, Bayesian network and deep neural network are used for timely detection and classification of APT-attacks on the NSL-KDD dataset. Moreover, 10-fold cross validation method is used to experiment these models. As a result, the accuracy (ACC) of the C5.0 decision tree, Bayesian network and 6-layer deep learning models is obtained as 95.64%, 88.37% and 98.85%, respectively, and also, in terms of the important criterion of the false positive rate (FPR), the FPR value for the C5.0 decision tree, Bayesian network and 6-layer deep learning models is obtained as 2.56, 10.47 and 1.13, respectively. Other criterions such as sensitivity, specificity, accuracy, false negative rate and F-measure are also investigated for the models, and the experimental results show that the deep learning model with automatic multi-layered extraction of features has the best performance for timely detection of an APT-attack comparing to other classification models., Comment: 38 pages, 15 figures, 5 tables

An efficient approach to improve the thermoelectric performance of materials is to converge their electronic bands, which is known as band engineering. In this regard, lots of effort have been made to further improve the thermoelectric efficiency of bulk and exfoliated monolayers of Bi$_{2}$Te$_{3}$ and Sb$_{2}$Te$_{3}$. However, ultra-high band degeneracy and thus significant improvement of power factor have not been yet realized in these materials. Using first-principles methods, we demonstrate that the valley degeneracy of Bi$_{2}$Te$_{3}$ and Sb$_{2}$Te$_{3}$ can be largely improved upon substitution of the middle layer Te atoms with the more electronegative S or Se atoms. Our detailed analysis reveals that in this family of materials two out of four possible valence band valleys merely depend on the electronegativity of the middle layer chalcogen atoms, which makes the independent modulation of the valleys position feasible. As such, band alignment of Bi$_{2}$Te$_{3}$ and Sb$_{2}$Te$_{3}$ largely improves upon substitution of the middle layer Te atoms with more electronegative, yet chemically similar, S and Se ones. A superior valence band alignment is attained in Sb$_{2}$Te$_{2}$Se monolayers where the three out of four possible valleys are well-aligned, resulting in a giant band degeneracy of 18 that holds the record among all thermoelectric materials., Comment: 8 pages, 5 figures

Improving the figure of merit $zT$ of thermoelectric materials requires simultaneously a high power factor and low thermal conductivity. An effective approach for increasing the power factor is to align the band extremum and achieve high band degeneracy ($\geq$ 12) near the Fermi level as realized in PbTe [\textcolor{blue}{Pei et. al. \textit{Nature} 473, 66 (2010)}], which usually relies on band structure engineering, e.g., chemical doping and strain. However, very few materials could achieve such a high band degeneracy without heavy doping or suffering impractical strain. By employing state-of-the-art first-principles methods with direct computation of phonon and carrier lifetime, we demonstrate that two new full-Heusler compounds Li$_2$TlBi and Li$_2$InBi, possessing a PbTe-like electronic structure, show exceptionally high power factors ($\sim$ 20 mWm$^{-1}$K$^{-2}$ at 300 K) and low lattice thermal conductivities (2.36 and 1.55 Wm$^{-1}$K$^{-1}$) at room temperature. The Tl$^{+}$Bi$^{3-}$ (In$^{+}$Bi$^{3-}$) sublattice forms a rock-salt structure, and the additional two valence electrons from Li atoms essentially make these compounds isovalent with Pb$^{2+}$Te$^{2-}$. The larger rock-salt sublattice of TlBi (InBi) shifts the valence band maximum from L point to the middle of the $\Sigma$ line, increasing the band degeneracy from fourfold to twelvefold. On the other hand, resonance bond in the PbTe-like sublattice and soft Tl-Bi (In-Bi) bonding interaction is responsible for intrinsic low lattice thermal conductivities. Our results present a novel strategy of designing high-performance thermoelectric materials.

A high power factor and low lattice thermal conductivity are two essential ingredients of highly efficient thermoelectric materials. Although monolayers of transition metal dichalcogenides possess high power factors, high lattice thermal conductivities significantly impede their practical applications. Our first-principles calculations show that these two ingredients are well fulfilled in the recently synthesized Pd$_{2}$Se$_{3}$ monolayer, whose crystal structure is composed of [Se$_{2}$]$^{2-}$ dimers, Se$^{2-}$ anions, and Pd$^{2+}$ cations coordinated in a square planar manner. Our detailed analysis of third-order interatomic force constants reveals that the anharmonicity and soft phonon modes associated with [Se$_2$]$^{2-}$ dimers lead to ultra-low lattice thermal conductivities in Pd$_{2}$Se$_{3}$ monolayers (1.5 and 2.9 Wm$^{-1}$K$^{-1}$ along the $a$- and $b$-axes at 300\,K respectively), which are comparable to those of high-performance bulk thermoelectric materials such as PbTe. Moreover, the "pudding-mold" type band structure, caused by Pd$^{2+}$ ($d^{8}$) cations coordinated in a square planar crystal field, leads to high power factors in Pd$_{2}$Se$_{3}$ monolayers. Consequently, both electron and hole doped thermoelectric materials with a considerably high $zT$ can be achieved at moderate carrier concentrations, suggesting that Pd$_{2}$Se$_{3}$ is a promising two-dimensional thermoelectric material., Comment: 6 pages, 5 figures, 1 tables

Intermetallic compounds with sizable band gaps are attractive for their unusual properties but rare. Here, we present a new family of stable semiconducting quaternary Heusler compounds, designed and discovered by means of high-throughput \textit{ab initio} calculations based on the 18-electron rule. The 99 new semiconductors reported here adopt the ordered quaternary Heusler structure with the prototype of LiMgSnPd (F$\bar{\mathbf{4}}$3m, No.\,216) and contain 18 valence electrons per formula unit. They are realized by filling the void in the half Heusler structure with a small and electropositive atom, i.e., lithium. These new stable quaternary Heusler semiconductors possess a range of band gaps from 0.3 to 2.5\,eV, and exhibit some unusual properties different from conventional semiconductors, such as strong optical absorption, giant dielectric screening, and high Seebeck coefficient, which suggest these semiconductors have potential applications as photovoltaic and thermoelectric materials. While this study opens up avenues for further exploration of this novel class of semiconducting quaternary Heuslers, the design strategy used herein is broadly applicable across a potentially wide array of chemistries to discover new stable materials., Comment: 8 pages, 6 figures

A new organic superconductor, possibly with formula $K_3$ p-terphenyl, has been discovered by Wang, Gao, Huang and Chen, reaching a very high $T_c$ of about 120~K. Besides a clear diamagnetic signal, most other details such as stoichiometry and structure are yet unknown. However, pristine p-terphenyl has a familiar $P2_1/a$ staggered bimolecular structure, and it can be reasonably assumed that a similar bimolecular structure could be retained by hypothetical $K_3$ p-terphenyl. We point out that the resulting 2-narrow band metal would support the same $s_{\pm}$ superconductivity recently proposed for doped polycyclic aromatic hydrocarbons such as La-phenanthrene or $K_3$-picene. In that model, narrow bands, a large Hubbard $U$ and the neighbourhood of a Mott transition enhance superconductivity rather than damaging it.

Elastic constants and their derived properties of various cubic Heusler compounds were calculated using first-principles density functional theory. To begin with, Cu$_2$MnAl is used as a case study to explain the interpretation of the basic quantities and compare them with experiments. The main part of the work focuses on Co$_2$-based compounds that are Co$_2$Mn$M$ with the main group elements $M=$~Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, and Co$_2TM$ with the main group elements Si or Ge, and the $3d$ transition metals $T=$~Sc, Ti, V, Cr, Mn, and Fe. It is found that many properties of Heusler compounds correlate to the mass or nuclear charge $Z$ of the main group element. Blackman's and Every's diagrams are used to compare the elastic properties of the materials, whereas Pugh's and Poisson's ratios are used to analyze the relationship between interatomic bonding and physical properties. It is found that the {\it Pugh's criterion} on brittleness needs to be revised whereas {\it Christensen's criterion} describes the ductile--brittle transition of Heusler compounds very well. The calculated elastic properties give hint on a metallic bonding with an intermediate brittleness for the studied Heusler compounds. The universal anisotropy of the stable compounds has values in the range of $0.57

In the present work, the elastic constants and derived properties of tetragonal and cubic Heusler compounds were calculated using the high accuracy of the full-potential linearized augmented plane wave (FPLAPW). To find the criteria required for an accurate calculation, the consequences of increasing the numbers of $k$-points and plane waves on the convergence of the calculated elastic constants were explored. Once accurate elastic constants were calculated, elastic anisotropies, sound velocities, Debye temperatures, malleability, and other measurable physical properties were determined for the studied systems. The elastic properties suggested metallic bonding with intermediate malleability, between brittle and ductile, for the studied Heusler compounds. To address the effect of off-stoichiometry on the mechanical properties, the virtual crystal approximation (VCA) was used to calculate the elastic constants. The results indicated that an extreme correlation exists between the anisotropy ratio and the stoichiometry of the Heusler compounds, especially in the case of Ni$_{2}$MnGa.

The synthesis of materials in high-pressure experiments has recently attracted increasing attention, especially since the discovery of record breaking superconducting temperatures in the sulfur-hydrogen and other hydrogen-rich systems. Commonly, the initial precursor in a high pressure experiment contains constituent elements that are known to form compounds at ambient conditions, however the discovery of high-pressure phases in systems immiscible under ambient conditions poses an additional materials design challenge. We performed an extensive multi component $ab\,initio$ structural search in the immiscible Fe--Bi system at high pressure and report on the surprising discovery of two stable compounds at pressures above $\approx36$ GPa, FeBi$_2$ and FeBi$_3$. According to our predictions, FeBi$_2$ is a metal at the border of magnetism with a conventional electron-phonon mediated superconducting transition temperature of $T_{\rm c}=1.3$ K at 40 GPa. In analogy to other iron-based materials, FeBi$_2$ is possibly a non-conventional superconductor with a real $T_{\rm c}$ significantly exceeding the values obtained within Bardeen-Cooper-Schrieffer (BCS) theory., Comment: 9 pages, 9 figures

The quantum physics of ions and electrons behind low-energy spectra of strongly correlated {\it molecular} conductors, superconductors and Mott insulators is poorly known, yet fascinating especially in orbitally degenerate cases. The fulleride insulator Cs$_{3}$C$_{60}$ (A15), one such system, exhibits infrared (IR) spectra with low temperature peak features and splittings suggestive of static Jahn-Teller distortions with breakdown of orbital symmetry in the molecular site. That is puzzling, for there is no detectable static distortion, and because the features and splittings disappear upon modest heating, which they should not. Taking advantage of the Mott-induced collapse of electronic wavefunctions from lattice-extended to nanoscale localized inside a caged molecular site, we show that unbroken spin and orbital symmetry of the ion multiplets explains the IR spectrum without adjustable parameters. This demonstrates the importance of a fully quantum treatment of nuclear positions and orbital momenta in the Mott insulator sites, dynamically but not statically distorted. The observed demise of these features with temperature is explained by the thermal population of a multiplet term whose nuclear positions are essentially undistorted, but whose energy is very low-lying. That term is in facts a scaled-down orbital excitation analogous to that of other Mott insulators, with the same spin $1/2$ as the ground state, but with a larger orbital moment of two instead of one., Comment: 6 pages, 3 figures

Semiconducting half- and, to a lesser extent, full-Heusler compounds are promising thermoelectric materials due to their compelling electronic properties with large power factors. However, intrinsically high thermal conductivity resulting in a limited thermoelectric efficiency has so far impeded their widespread use in practical applications. Here, we report the computational discovery of a class of hitherto unknown stable semiconducting full-Heusler compounds with ten valence electrons ($X_2YZ$, $X$=Ca, Sr, and Ba; $Y$= Au and Hg; $Z$=Sn, Pb, As, Sb, and Bi) through high-throughput $ab-initio$ screening. These new compounds exhibit ultralow lattice thermal conductivity $\kappa_{\text{L}}$ close to the theoretical minimum due to strong anharmonic rattling of the heavy noble metals, while preserving high power factors, thus resulting in excellent phonon-glass electron-crystal materials., Comment: 6 pages, 5 figures

Solid CS$_{2}$ is superficially similar to CO$_{2}$, with the same $Cmca$ molecular crystal structure at low pressures, which has suggested similar phases also at high pressures. We carried out an extensive first principles evolutionary search in order to identify the zero temperature lowest enthalpy structures of CS$_{2}$ for increasing pressure up to 200\,GPa. Surprisingly, the molecular $Cmca$ phase does not evolve into $\beta$-cristobalite as in CO$_{2}$, but transforms instead into phases HP2 and HP1, both recently described in high pressure SiS$_{2}$. HP1 in particular, with a wide stability range, is a layered $P2_{1}/c$ structure characterized by pairs of edge-sharing tetrahedra, and theoretically more robust than all other CS$_{2}$ phases discussed so far. Its predicted Raman spectrum and pair correlation function agree with experiment better than those of $\beta$-cristobalite, and further differences are predicted between their respective IR spectra. The band gap of HP1-CS$_{2}$ is calculated to close under pressure yielding an insulator-metal transition near 50 GPa in agreement with experimental observations. However, the metallic density of states remains modest above this pressure, suggesting a different origin for the reported superconductivity., Comment: 8 pages, 8 figures

The damaging effect of strong electron-electron repulsion on regular, electron-phonon %$s$-wave superconductivity is a standard tenet. In spite of that, an increasing number of compounds such as fullerides and more recently alkali-doped aromatics exhibit %$s$-wave or presumably $s$ wave superconductivity despite very narrow bands and very strong electron repulsion. Here, we explore superconducting solutions of a model Hamiltonian inspired by the electronic structure of alkali doped aromatics. The model is a two-site, two-narrow-band metal with a single intersite phonon, leading to attraction-mediated, two-order parameter superconductivity. On top of that, the model includes a repulsive on-site Hubbard $U$, whose effect on the superconductivity we study. Starting within mean field, we find that $s \pm$ superconductivity is the best solution surviving the presence of $U$, whose effect is canceled out by the opposite signs of the two order parameters. The correlated Gutzwiller study that follows is necessary because without electron correlations the superconducting state would in this model be superseded by an antiferromagnetic insulating state with lower energy. The Gutzwiller correlations lower the energy of the metallic state, with the consequence that the $s \pm$ superconducting state is stabilized and even strengthened for small Hubbard $U$.

Alkali doped aromatic compounds have shown evidence of metallic and superconducting phases whose precise nature is still mysterious. In potassium and rubidium doped phenanthrene, superconducting temperatures around 5 K have been detected, but such basic elements as the stoichiometry, crystal structure, and electronic bands are still speculative. We seek to predict the crystal structure of M3-phenanthrene (M = K, Rb) using ab-initio evolutionary simulation in conjunction with density functional theory (DFT), and find metal but also insulator phases with distinct structures. The original P21 herringbone structure of the pristine molecular crystal is generally abandoned in favor of different packing and chemical motifs. The metallic phases are frankly ionic with three electrons acquired by each molecule. In the nonmagnetic insulating phases the alkalis coalesce reducing the donated charge from three to two per phenanthrene molecule. A similar search for K3-picene yields an old and a new structure, with unlike potassium positions and different electronic bands, but both metallic retaining the face-to-edge herringbone structure and the P21 symmetry of pristine picene. Both the new K3-picene and the best metallic M3-phenanthrene are further found to undergo a spontaneous transition from metal to antiferromagnetic insulator when spin polarization is allowed, a transition which is not necessarily real, but which underlines the necessity to include correlations beyond DFT. Features of the metallic phases that may be relevant to phonon-driven superconductivity are underlined., Comment: 14 pages, 9 figures, 1 table, and supplementary information

Several examples of metallic electron doped polycyclic aromatic hydrocarbons (PAHs) molecular crystals have recently been experimentally proposed. Some of them have superconducting components, but most other details are still unknown beginning with structure and the nature of metallicity. We carried out ab-initio density functional calculations for La-Phenanthrene (La-PA), here meant to represent a generic case of three-electron doping, to investigate structure and properties of a conceptually simple case. To our surprise we found first of all that the lowest energy state is not metallic but band insulating, with a disproportionation of two inequivalent PA molecular ions and a low P1 symmetry, questioning the common assumption that three electrons will automatically metallize a PAH crystal. Our best metallic structure is metastable and slightly higher in energy, and retains equivalent PA ions and a higher P21 symmetry -- the same generally claimed for metallic PAHs. We show that a "dimerizing" periodic distortion opens very effectively a gap in place of a symmetry related degeneracy of all P21 structures near the Fermi level, foreshadowing a possible role of that special intermolecular phonon in superconductivity of metallic PAHs. A Hubbard-Frohlich model describing that situation is formulated for future studies., Comment: 9 pages and 7 figures

Functionalized polcyclic aromatic hydrocarbons (PAHs) are an interesting class of molecules in which the electronic state of the graphene-like hydrocarbon part is tuned by the functional group. Searching for new types of donor and acceptor molecules, a set of new PAHs has recently been investigated experimentally using ultraviolet photoelectron spectroscopy (UPS). In this work, the electronic structure of the PAHs is studied numerically with the help of B3LYP hybrid density functionals. Using the DELTA-SCF method, electron binding energies have been determined which affirm, specify and complement the UPS data. Symmetry properties of molecular orbitals are analyzed for a categorization and an estimate of the related signal strength. While SIGMA-like orbitals are difficult to detect in UPS spectra of condensed film, calculation provides a detailed insight into the hidden parts of the electronic structure of donor and acceptor molecules. In addition, a diffuse basis set (6-311++G**) was used to calculate electron affinity and LUMO eigenvalues. The calculated electron affinity (EA) provides a classification of the donor/acceptor properties of the studied molecules. Coronene-hexaone shows a high EA, comparable to TCNQ, which is a well-known classical acceptor. Calculated HOMO-LUMO gaps using the related eigenvalues have a good agreement with the experimental lowest excitation energies. TD-DFT also accurately predicts the measured optical gap., Comment: Journal of Molecular Spectroscopy, 20 pages, 2 figures, 3 tables, 48 references

We present a systematic study of the high-pressure FeSe phase performed by means of the first-principle electronic structure calculations. Basing on available experimental information about the unit cell geometry we calculate the band structure and characterize the related properties during their pressure driven evolution. The electronic structure including the hybrid functional B3LYP or the Hubbard parameter U for the iron d states lead to the correct semiconducting ground state for the hexagonal stoichiometric FeSe within the broad pressure range (up to 30 GPa).