Tight-binding Research Articles

Seebeck Effect of Dirac Electrons in Organic Conductors under Hydrostatic Pressure Using a Tight-Binding Model Derived from First Principles

Seebeck Effect of Dirac Electrons in Organic Conductors under Hydrostatic Pressure Using a Tight-Binding Model Derived from First Principles

Signature of excitonic insulators in phosphorene nanoribbons.

Phosphorene is a recently developed two-dimensional (2D) material that has attracted tremendous attention because of its unique anisotropic optical properties and quasi-one-dimensional (1D) excitons. We use first-principles calculations combined with the maximally localized Wannier function tight binding Hamiltonian (MLWF-TB) and Bethe-Salpeter equation (BSE) formalism to investigate quasiparticle effects of 2D and quasi-1D blue and black phosphorene nanoribbons. Our electronic structure calculations shows that both blue and black monolayered phases are semiconductors. On the other hand black phosphorene zigzag nanoribbons are metallic. Similar behavior is found for very thin blue phosphorene zig-zag and armchair nanoribbon. As a general behavior, the exciton binding energy decreases as the ribbon width increases, which highlights the importance of quantum confinement effects. The solution of the BSE shows that the blue phosphorene monolayer has an exciton binding energy four times higher than that of the black phosphorene counterpart. Furthermore, both monolayers show a different linear optical response with respect to light polarization, as black phosphorene is highly anisotropic. We find a similar, but less pronounced, optical anisotropy for blue phosphorene monolayer, caused exclusively by the quasi-particle effects. Finally, we show that some of the investigated nanoribbons show a spin-triplet excitonic insulator behavior, thus revealing exciting features of these nanoribbons and therefore provides important advances in the understanding of quasi-one dimensional phosphorus-based materials.&#xD.

Long-range Pairing in Monolayer NbSe2 Facilitates the Emergence of Topological Superconducting States

Abstract NbSe2, which simultaneously exhibits superconductivity and spin-orbit coupling, is anticipated to pave the way for topological superconductivity and unconventional electron pairing. In this paper, we systematically study topological superconducting (TSC) phases in monolayer NbSe2 through mixing on-site s-wave pairing (ps) with long-range pairing (psA1) based on a tight-binding model. We observe rich phases with both fixed and sensitive Chern numbers (CNs) depending on the chemical potential (μ) and out-of-plane magnetic field (Vz). As psA1 increases, the TSC phase manifests matching and mismatching features according to whether there is a bulk-boundary correspondence (BBC). Strikingly, the introduction of long-range pairing significantly reduces the critical Vz to form TSC phases compared with the pure s-wave paring. Moreover, the TSC phase can be modulated even at Vz=0 under appropriate μ and psA1, which is identified by the robust topological edge states (TESs) of ribbons. Additionally, the long-range pairing influences the hybridization of bulk and edge states, resulting in a matching/mismatching BBC with localized/oscillating TESs on the ribbon. Our finding is helpful for realization of TSC states in experiment, as well as designing and regulating TSC materials.

The Role of Spin – Orbit Coupling in the Spin Transport FM-(G/C)N-FM

The spin transport through DNA system formed by a guanine-cytosine is studied extendedly in our work. Hence, theoretical treatment is accomplished for one magnetized active region (includes base pairs and backbone) coupled to ferromagnetic leads in parallel configuration case, throughout magnetic quantum contacts (FM-(G/C)N-FM). Our treatment is based on the tight binding model to derive obvious formula for the spin dependent transmission spectrum which is employed to investigate the spin transport through DNA junction. Our calculations are accomplished in the presence of spin-orbit coupling for strong, weak and "without backbone" regimes. The role the system spin dependent factors of the transport of (G/C)N molecule are investigated in our study. These factors include the molecular length, as well as externally applied bias voltage. Variation of these factors can enhance or suppress spin transport through (G/C)N molecule (with N=10,15,20,25. The transmission spectrum results confirm that the spin transport throughout (G/C)N is originated by a coherent tunneling process between neighboring bases through the overlapping of the LUMO orbitals of the bases. The physical mechanism is raise from quantum interference combination with molecular length and the presence of spin-orbit coupling. The best functional feature for environmental effect, which may induce dephasing such as leads temperature, is investigated. The results showed that the spin-polarized transport can be effectively regulated by the molecular length of (G/C) which can exhibit efficient spin filtering and spin switching

Magic-angle twisted bilayer graphene under orthogonal and in-plane magnetic fields

We investigate the effect of a magnetic field on the band structure of bilayer graphene with a magic twist angle of 1.08∘. The coupling of a tight-binding model and the Peierls phase allows the calculation of the energy bands of periodic two-dimensional systems. For an orthogonal magnetic field, the Landau levels are dispersive, particularly for magnetic lengths comparable to or larger than the twisted bilayer cell size. A high in-plane magnetic field modifies the low-energy bands and gap, which we demonstrate to be a direct consequence of the minimal coupling.

Electronic heat conductivity in a two-temperature state

Heat transport in solids is governed by two fundamental contributions, atomic and electronic. The electronic energy transport in transient excited states is a defining factor in the problem of ultrafast material irradiation. Here, we calculate the electronic heat conductivity at elevated electron temperatures up to 40,000 K. We apply the novel combined method of tight binding formalism to calculate the electron-phonon contribution to the electronic heat conductivity, and the linear response theory (in the single-pole Ritchie-Howie loss function approximation) for its electron-electron counterpart, implemented in the hybrid code XTANT-3. It allows us to evaluate the electronic heat conductivity in a wide range of materials – fcc metals: Al, Ca, Ni, Cu, Sr, Y, Zr, Rh, Pd, Ag, Ir, Pt, Au, and Pb; hcp metals: Mg, Sc, Ti, Co, Zn, Tc, Ru, Cd, Hf, Re, and Os; bcc metals: V, Cr, Fe, Nb, Mo, Ba, Ta, and W; other metals: Sn, Ga, In, Mn, Te, and Se; semimetal graphite; semiconductors – group IV: Si, Ge, and SiC; group III-V: AlAs, AlP, GaP, GaAs, and GaSb; oxides: ZnO, TiO2, and Cu2O; and others: PbI2, ZnS, and B4C.

A DFTB study on the electronic response of encapsulated DNA nucleobases onto chiral CNTs as a sequencer

Sequencing the DNA nucleobases is essential in the diagnosis and treatment of many diseases related to human genes. In this article, the encapsulation of DNA nucleobases with some of the important synthesized chiral (7, 6), (8, 6), and (10, 8) carbon nanotubes were investigated. The structures were modeled by applying density functional theory based on tight binding method (DFTB) by considering semi-empirical basis sets. Encapsulating DNA nucleobases on the inside of CNTs caused changes in the electronic properties of the selected chiral CNTs. The results confirmed that van der Waals (vdW) interactions, π-orbitals interactions, non-bonded electron pairs, and the presence of high electronegative atoms are the key factors for these changes. The result of electronic parameters showed that among the CNTs, CNT (8, 6) is a suitable choice in sequencing guanine (G) and cytosine (C) DNA nucleobases. However, they are not able to sequence adenine (A) and thymine (T). According to the band gap energy engineering approach and absorption energy, the presence of G and C DNA nucleobases decreased the band gap energy of CNTs. Hence selected CNTs suggested as biosensor substrates for sequencing G and C DNA nucleobases.

Influence of the disorder correlation length on localization and quantum state transference in tight-binding channels

We investigate in detail the transference of quantum states in a disordered channel. We consider a one-dimensional tight-binding model consisting of a source S connected to a receiver R throughout a disordered channel. The disorder distribution contains a single tunable spatial correlation length. We demonstrate that the disorder correlation length plays a relevant role within the localization properties of the channel. The hopping parameter between the sites S and R and the channel are also adjustable parameters. We investigate the possibility of transference of quantum states along this quantum channel model and describe the optimal conditions for the occurrence of a high fidelity process.

From topological nodal-line semimetals to quantum spin Hall insulators in tetragonal SnX monolayers (X=F, Cl, Br, I)

Abstract Two-dimensional (2D) topological materials have recently garnered significant interest due to their profound physical properties and promising applications for future quantum nanoelectronics. Achieving various topological states within one type of materials is, however, seldom reported. Based on first-principles calculations and tight-binding models, we investigate topological electronic states in a novel family of 2D halogenated tetragonal stanene (T-SnX, X = F, Cl, Br, I). All the four monolayers are found being unusual topological nodal-line semimetals (NLSs), protected by a glide mirror symmetry. When spin-orbit coupling (SOC) is turned on, T-SnF and TSnCl are still ascertained as topological NLSs due to the remaining band inversion, primarily composed of Sn pxy orbitals, while T-SnBr and T-SnI become quantum spin Hall insulators. The phase transition is ascribed to moving up in energy of Sn s orbitals and increasing of SOC strengths. The topology origin in the materials is uniformly rationalized through elementary band representations. The robust and diverse topological states found in the 2D T-SnX monolayers position them as an excellent material platform for the development of innovative topological electronics.

Gate-Tunable Asymmetric Quantum Dots in Graphene-Based Heterostructures: Pure Valley Polarization and Confinement

We explore the possibility of attaining valley-dependent tunnelling and confinement using proximity-induced spin-orbit couplings (SOCs) in graphene-based heterostructures. We consider gate-tunable asymmetric quantum dots (AQDs) on graphene heterostructures and exhibiting a C3v and/or C6v symmetry. By employing a tight-binding model, we explicitly reveal a pure valley confinement and valley signal in AQDs by streaming the valley local density, leading to valley-charge separation in real space. The confinement of the valley quasi-bound states is sensitive to the locally induced SOCs and to the spatial distribution of the induced AQDs; it is also robust against on-site disorder. The adopted process of attaining a pure valley-Hall conductivity and confinement with zero charge currents is expected to provide more options towards valley-dependent electron optics.

Implementation of the Su-Schrieffer-Heeger Model in the Self-Assembly Si-In Atomic Chains on the Si(553)-Au Surface.

Indium-decorated Si atomic chains on a stepped Si(553)-Au substrate are proposed as an extended Su-Schrieffer-Heeger (SSH) model, revealing topological end states. An appropriate amount of In atoms on the Si(553)-Au surface induce the self-assembly formation of trimer SSH chains, where the chain unit cell comprises one In atom and two Si atoms, confirmed by scanning tunneling microscopy images and density functional calculations. The electronic structure of the system, examined through scanning tunneling spectroscopy, manifests three electron bands within the Si-In chain, accompanied by additional midgap topological states exclusively appearing at the chain's end atoms. To elucidate the emergence of these topological states, a tight-binding model for a finite-length-extended SSH chain is proposed. Analysis of the energy spectra, density of states functions, and eigenfunctions demonstrates the topological nature of these self-assembled atomic chains.

Benchmark Investigation of SCC-DFTB against Standard and Hybrid DFT to Model Electronic Properties in Two-Dimensional MOFs for Thermoelectric Applications.

Recent studies have shown that metal-organic frameworks (MOFs) have potential as thermoelectric materials, and the topic has received increasing attention. The main motivation for this project is to further our knowledge of thermoelectric properties in MOFs and find which available self-consistent-charge density functional tight binding (SCC-DFTB) method can best predict (at least trends in) the electronic properties of MOFs at a lower computational cost than standard density functional theory (DFT). In this work, the electronic properties of monolayer, serrated, AA-stacked, and/or AB-stacked Zn3C6O6, Cd3C6O6, Zn-NH-MOF─for which no previous calculations of thermoelectric performance exist─and Ni3(HITP)2 MOFs are modeled with DFT-PBE, DFT-HSE06, GFN1-xTB, GFN2-xTB, and DFTB-3ob/mio. The band structures, density of states, and their relative orbital contributions, as well as the electrical conductivity, Seebeck coefficient, and power factor, are compared across methods and geometries. Our results suggest that GFN-xTB is adequate to predict the MOFs' band structure shape and density of states but not band gap. Our calculations further indicate that Zn3C6O6, Cd3C6O6, and Zn-NH-MOF have higher power factor values than Ni3(HITP)2, one of the highest performing synthesized MOFs, and are therefore promising for thermoelectric applications.

Exploring ZnO nanoparticles: UV–visible analysis and different size estimation methods

The study investigates several theoretical and empirical methods for determining the size of zinc oxide nanoparticles (ZnO NPs) and studies their characteristics by using solely UV–visible spectroscopy. The investigation begins with the green synthesis of three samples of ZnO NPs using three different reducing agents Aspergillus Niger fungal biomass (AN), Aloe barbadensis Mille (ABM) and Ocimum tenuiflorum (OT) leaves, respectively with Zinc Sulphate as a precursor involving precipitation method. The study analyses the UV–visible data of each sample to obtain optical bandgap, Urbach energy, refractive index, optical conductivity. and apply several methods or Models such as Effective Mass Approximation (EMA) or Brus Equation (BE), Hyperbolic Band Model (HBM), Meulenkamp's Expression (ME), Tight Binding Model (TBM) and a simplified version of EMA (SEMA) to estimate the size of ZnO NPs. The effectiveness of size-determining models was assessed using two sets of one-way analysis of variance (ANOVA) for each ZnO sample and models Followed by Tukey post-hoc analysis to identify the exact sample that is different from other samples.

Numerical simulation of Rashba spin–orbit coupling effect on quantum Hall resistivity within tight-binding approximation

A numerical simulation of the effect of Rashba spin–orbit coupling (RSO) on quantum transport properties of electrons confined to a two-dimensional electron gas (2DEG) in the integer quantum Hall regime is presented. The mechanism of quantization and the dependence of the Hall resistivity (HR) on the system built-in and external parameters are studied using the non-equilibrium Green’s function (NEGF) technique. Relevant Green’s functions are computed numerically using spectral decomposition method in combination with recursive techniques. The tight-binding-like representation of the system Hamiltonian including magnetic field is obtained within the finite difference method, using Dirichlet boundary conditions. Corresponding formula linking the Hall resistivity with the transmission function of the system has been derived analytically within the NEGF formalism in a general form, in the sense that the formula can also be used beyond the linear response limit and for nonzero temperatures. In particular, it was shown explicitly that in the presence of the RSO coupling the even- and odd plateaus emerging in the magnetic-field dependence of the quantum Hall resistivity are related to different physical mechanisms.

Optical snake states in a photonic graphene.

We propose an optical analog of electron snake states based on an artificial gauge magnetic field in a photonic graphene implemented by varying distances between cavity pillars. We develop an intuitive and exhaustive continuous model based on tight-binding approximation and compare it with numerical simulations of a realistic photonic structure. The allowed lateral propagation direction is shown to be strongly coupled to the valley degree of freedom, and the proposed photonic structure may be used as a valley filter.

BerryEasy: A GPU enabled python package for diagnosis ofnth-order and spin-resolved topology in the presence of fields and effects.

Multiple software packages currently exist for the computation of bulk topological invariants in both idealized tight-binding models and realistic Wannier tight-binding models derived from density functional theory. Currently, only one package is capable of computing nested Wilson loops and spin-resolved Wilson loops. These state-of-the-art techniques are vital for accurate analysis of band topology. In this paper we introduce BerryEasy, a python package harnessing the speed of graphical processing units to allow for efficient topological analysis of supercells in the presence of disorder and impurities. Moreover, the BerryEasy package has built-in functionality to accommodate use of realistic many-band tight-binding models derived from first-principles.

Inverse Optically-Induced Ring Currents in Ring-Shaped Molecules.

Permanent electronic ring currents are supported within manifolds of ΓE degenerate excited electronic states as E± = Ex ± iEy excitations. In [ Phys. Rev. Res. 2021, 3, L042003] we showed the existence of inverse-current manifolds, where the direction of the electronic ring current in each degenerate state E± is opposite to the circular polarization of the generating light fields. This vibronic effect is caused by the exchange of orbital angular momentum between the electrons and the vibrational modes with the required symmetry. Here we consider the case of fixed nuclei and find that ring-shaped molecular systems possess inverse-current manifolds on a purely electronic-structure basis, i.e., without intervention of vibronic coupling. The effect is explained first on a tight-binding model with cyclic symmetry and then considering the ab initio electronic structure of benzene and sym-triazine. A framework for discriminating regular- and inverse-current ΓE manifolds in molecules using quantum chemistry calculations is provided.

Simple model for the gap in the surface states of the antiferromagnetic topological insulator MnBi[formula omitted]Te[formula omitted]

We study the influence of the antiferromagnetic order on the surface states of topological insulators. We derive an effective Hamiltonian for these states, taking into account the spatial structure of the antiferromagnetic order. We obtain a typical (gapless) Dirac Hamiltonian for the surface states when the surface of the sample is not perturbed. Gapless spectrum is protected by the combination of time-reversal and half-translation symmetries. However, a shift in the chemical potential of the surface layer opens a gap in the spectrum away from the Fermi energy. Such a gap occurs only in systems with finite antiferromagnetic order. We observe that the system topology remains unchanged even for large values of the disorder. We calculate the spectrum using the tight-binding model with different boundary condition. In this case we get a gap in the spectrum of the surface states. This discrepancy arises due to the violation of the combined time-reversal symmetry. We compare our results with experiments and density functional theory calculations.

Abstract PO3-26-09: A novel class of RNR inhibitors that induces genomic instability and breast cancer cell death without inducing overt toxicities

Abstract Despite the development of screening techniques and therapies, nearly 30% of breast cancers progress to Stage IV metastatic disease. These advanced cancers are highly proliferative, engaging in ongoing DNA synthesis that requires ribonucleotide reductase (RNR), the rate-limiting enzyme for dNTP synthesis. RRM2, the small subunit of RNR, activates the enzyme, increases deoxynucleotide pools, and is overexpressed in many cancers, including breast cancer. Thus, RNR is an established therapeutic target in advanced breast cancer. Currently, gemcitabine is the only FDA-approved RNR inhibitor used to treat Stage IV disease. As a nucleoside analog, gemcitabine also causes severe dose-limiting toxicities (i.e. myelosuppression and hepatotoxicity) due to off-target DNA replication termination. We hypothesize that a novel, non-nucleoside, RNR inhibitor may overcome these limitations. To address this, we developed TMU27a, a derivative of naphthyl salicylic acyl hydrazone (NSAH), which was identified in an in silico screen for its high-affinity binding to the RNR catalytic site. To measure direct interactions between TMU27a and purified RNR protein, we used surface plasmon resonance, revealing on-target, tight binding (Kd = 150 nM). Unbiased docking and molecular dynamics simulations (using lowest energy calculations) predicted the binding sight of TMU27a to be the catalytic site of RNR, where it is stabilized through extensive interactions formed with conserved residues. Preliminary docking predictions also indicate multiple clash sites between TMU27a and the DNA polymerase lambda nucleotide pocket even in the lowest energy pose (unlike gemcitabine), suggesting that TMU27a inhibits RNR activity through a novel mechanism without significant off-target binding to other nucleotide binding proteins that contribute to toxicity. Demonstrating on-target inhibition, TMU27a reduces dATP levels and induces S and G2/M-phase stalling, leading to significant DNA damage and chromosomal instability. This excessive genomic damage causes growth repression, apoptosis, and senescence in several triple negative breast cancer (TNBC) cell lines. In xenograft mouse models of TNBC, TMU27a fully suppressed tumor growth without impacting mouse weight, suggesting strong drug efficacy in the absence of overt toxicity. Moreover, while short-term exposure to gemcitabine suppresses red and white blood cell populations, TMU27a does not. Together, these data indicate that TMU27a and its potential analogs are novel, non-toxic RNR inhibitors that overcome the limitations of gemcitabine for treating breast cancer. We are currently investigating how and where TMU27a binds human RNR using cryo-electron microscopy with the goal of generating a novel class of RNR inhibitors through structure-based drug design, improving binding affinity and selectivity. Citation Format: Taylor Baker, Kristen Weber-Bonk, Wei Huang, Derek Taylor, Ruth Keri. A novel class of RNR inhibitors that induces genomic instability and breast cancer cell death without inducing overt toxicities [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO3-26-09.

Semimetallic state transition in Two-Dimensional carbon nitride covalent networks and enhanced electrocatalytic activity for nitrate to ammonia conversion

Single-atom catalysts (SACs), due to their maximum atomic utilization rate, show tremendous potential for application in the electrocatalytic synthesis of ammonia from nitrate. Yet, the development of superior supports that preserve the high selectivity, activity, and stability of SACs remains an imperative challenge. In this work, based on first-principles calculations and tight-binding (TB) model analysis, a new two-dimensional (2D) carbon nitride monolayer, C7N6, is proposed. The C7N6 structure exhibits a strong covalent network, with dynamical, thermal, and mechanical stability. Surprisingly, the structural transition from C9N4 to C7N6 corresponds to a semimetallic state transition. Further symmetry analysis unveils that the Dirac states in C7N6 are protected by space–time inversion symmetry, and the physical origin of the Dirac cone was confirmed using the TB model. Additionally, a non-zero Z2 invariant and significant topological edge states demonstrate its topologically nontrivial nature. Considering the excellent structural and topological properties of C7N6, a three-step screening strategy is designed to identify eligible SACs for electrochemical nitrate reduction reaction (NO3RR), and Ti@C7N6 is identified as possessing the best activity, with the last proton-electron coupling step *NH2→*NH3 being the potential-determining step (PDS), for which the limiting potential is 0.48 V. Moreover, a free energy diagram shows that the *NOH reaction pathway is energetically preferred on Ti@C7N6, and ab initio molecular dynamics (AIMD) calculations at 500 K confirm its good thermal stability. Our study not only provides excellent CN-based support material but also offers theoretical guidance for constructing highly active and selective SACs for nitrate reduction.