One-electron States Research Articles

Development of novel DNA aptamers and colorimetric nanozyme aptasensor for targeting multi-drug-resistant, invasive Salmonella typhimurium strain SMC25

Invasive, biofilm-forming Non-typhoidal Salmonella (iNTS), propagating through the global food and water supply chain, presents a significant risk to food safety and public health. Developing a robust detection system is crucial for enabling point-of-care, affordable, and equipment-free identification of this pathogen throughout the supply chain. In this study, we screened a novel pool of ssDNA aptamers specific to a multidrug resistant iNTS strain SMC25, previously isolated from Indian poultry products in our earlier research. Through 13 rounds of whole-cell SELEX, we identified, characterized, and selected seven full-length aptamers (ST18, ST19, ST25, ST28, ST29, ST31, and ST32). Flow cytometric analysis reveals superior binding of ST25, ST28, ST29, and ST31. These aptamers were translated onto Nanozyme-based aptasensing system for efficient, cost-effective detection of SMC25. This system harnesses the aptamer-mediated, reversible peroxidase-like activity of gold nanoparticles (GNPs) to oxidize the TMB substrate into a one-electron oxidation state, resulting in a blue-colored Diamine charge transfer complex (DCTC). The catalytic process, coupled with GNP aggregation, induces a visible color change in the test mixture from ruby-red to blue. Post-SELEX truncations identified the optimal aptamer sequence (T_ST31), which selectively detected SMC25 in water with a limit of detection (LOD) of ∼10⁴ CFU/mL. Lower concentrations (10 CFU/mL) of SMC25 could be detected after non-selective enrichment within 120 min. This research introduces a novel pool of iNTS-specific aptamers along with a cost-effective (0.25 USD per sample) solution for colorimetric detection by the naked eye.

Shape and quantum size effects on the electronic structure, oscillator strengths and state lifetimes of helium-like quantum dots

Transition energies, electric static polarizability, oscillator strengths and state lifetimes of helium-like quantum dots are determined as a function of their shape and size. A configuration interaction approach based on B-spline functions is used. We found that, the oscillator strengths present an extremum around a low value of the dot radius whatever the shape of the confining potential. This extremum is due to the pressure on the energy levels in such a way that for a particular value of the dot radius, the second electron in the excited one-electron state reaches the borders of the confinement potential. The extremum position depends on the impurity charge and the oscillator strength value at this point changes with the potential well shape. As well, the increase of the effective mass involves the shift of the position of the oscillator strength extremum towards weak radius values. The first excited state lifetime globally increases with the dot radius and the reduction of the nuclear charge but presents a shoulder for a certain low value of the dot radius mostly marked for a triangular form of the confining potential.

Electronic State of Arsenic <i>endo</i>-atom and indices of interatomic bonds in[As@Ni<sub>12</sub>As<sub>20</sub>]<sup>3-/0</sup>, As<sub>20</sub>, Ni<sub>12</sub>As<sub>20</sub>, As@C<sub>60</sub>, and As@C<sub>70</sub> Clusters

The DFT PBE0/SDD method was used to calculate bond lengths and bond indices in As20, Ni12As20, [As@Ni12As20]3-, As@C60 and As@C70 clusters. The degrees of oxidation and reduction of the endo -atom and the shell are expressed in terms of the populations of one-electron states localized in these components of the complexes. Each As atom in clusters has a entirely localized lone electron pair. The arsenic atom inside fullerenes retains the electronic configuration and spin of the ground state of the free As atom. Inside the [Ni12As20]6- shell, it has an oxidation state of 3+. There is no covalent bond between the endo -atom and the shell in clusters. The bond indices refute the opinion about the “onion” structure of [As@Ni12@As20]3-: the nickel atoms are not bonded to each other, the As-As bond indices are three times lower than in As20.

Large-bias spectroscopy of Yu-Shiba-Rusinov states in a double quantum dot

We have performed tunnel transport spectroscopy on a quantum dot (QD) molecule proximitized by a superconducting contact. In such a system, the scattering between QD spins and Bogoliubov quasiparticles leads to the formation of Yu-Shiba-Rusinov (YSR) states within the superconducting gap. In this work, we investigate interactions appearing when one- and two-electron spin states in a double-QD energetically align with the superconducting gap edge. We find that the inter-dot spin-triplet state interacts considerably stronger with the superconductor than the corresponding singlet, pointing to stronger screening. By forming a ring molecule with a significant orbital contribution to the effective g-factor, we observe interactions of all four spin-orbital one-electron states with the superconductor under a weak magnetic field.

Characterization of helical states in semiconductor quantum wells using quantum information quantities

The information content of one-electron bulk and edge states in semiconductor quantum wells is calculated in the inverted regime, where edge states, topologically protected, are responsible for the conduction in Spin Quantum Hall effect experiments. To study the information content of these states we first calculate realistic two dimensional one-electron states, solving first the eight-band $\mathbf{k}\cdot\mathbf{p}$ Hamiltonian to obtain the bulk states and then a four band effective Hamiltonian to obtain the edge states. The behavior of information-like quantities, as a function of the different parameters that define the quantum well, is analyzed. The results presented show that the helical edge states can be singled out using different quantities that characterize the rich phenomenology of these states.

Machine Learning Approach to Calculate Electronic Couplings between Quasi-diabatic Molecular Orbitals: The Case of DNA.

Diabatization of one-electron states in flexible molecular aggregates is a great challenge due to the presence of surface crossings between molecular orbital (MO) levels and the complex interaction between MOs of neighboring molecules. In this work, we present an efficient machine learning approach to calculate electronic couplings between quasi-diabatic MOs without the need of nonadiabatic coupling calculations. Using MOs of rigid molecules as references, the MOs that can be directly regarded to be quasi-diabatic in molecular dynamics are selected out, state tracked, and phase corrected. On the basis of this information, artificial neural networks are trained to characterize the structure-dependent onsite energies of quasi-diabatic MOs and the intermolecular electronic couplings. A representative sequence of DNA is systematically studied as an illustration. Smooth time evolution of electronic couplings in all base pairs is obtained with quasi-diabatic MOs. In particular, our method can calculate electronic couplings between different quasi-diabatic MOs independently, and thus, this possesses unique advantages in many applications.

Origin of symmetry-forbidden high-order harmonic generation in the time-dependent Kohn-Sham formulation

We find, for two-electron closed-shell systems (${\mathrm{H}}_{2}$ molecule, $\mathrm{He}$ atom), symmetry-forbidden peaks in the high-order harmonic spectra obtained by the time-dependent Kohn-Sham equations, and clarify their origin. It turns out that fixation of the number of Kohn-Sham orbitals and their occupations gives rise to unphysical transition paths and, therefore, incorrect populations of the one-electron excited states, which leads to even-order harmonics in systems with inversion symmetry. We show that the time-dependent natural Kohn-Sham and time-dependent configuration interaction equations do not suffer from this shortcoming.

Thia-Bridged Triarylamine[4]helicene-Functionalized Polynorbor­nenes as Redox-Active pH-Sensitive Polymers

AbstractA series of thia-bridged triarylamine[4]helicene-functionalized polynorbornenes P1, P2, and P3 were synthesized via ring-opening metathesis polymerization (ROMP). The polymers obtained undergo a reversible one-electron oxidation, in both solution and solid state, responding to the pH changes in the surrounding medium showing a clear reversible electrochromic behavior.

Excitation of Some Nitrogen-Like Ions: Calculations and Comparison with Measurements

Electronic energies of one-electron excited states 1s22s22p2ns 4P, 1s22s22p2ns 2P, 1s22s22p2np 4S, 1s22s22p2np 2S, 1s22s22p2np 4P, 1s22s22p2np 2P, 1s22s22p2np 4D, 1s22s22p2np 2D, 1s22s22p2nd 4P, 1s22s22p2nd 2P, 1s22s22p2nd 4D, 1s22s22p2nd 2D, 1s22s22p2nd 4F, 1s22s22p2nd 2F of nitrogen-like ions with n=3-12 and Z=7-50 have been calculated. For all the aforementioned electronic configurations, fine-structure levels have been determined for states with different total momentum J. The comparison of theoretical results with the available experimental data shows that theory and measurements agree well. In particular, relative accuracy of 10-4 has been achieved in the electronic energy of N-like at Z > 10, while the typical deviation in the calculated fine-structure levels from experimental data is in the order of 10-2

Behavior of the Energy Spectrum and Electric Conduction of Doped Graphene.

We consider the effect of atomic impurities on the energy spectrum and electrical conductance of graphene. As is known, the ordering of atomic impurities at the nodes of a crystal lattice modifies the graphene spectrum of energy, yielding a gap in it. Assuming a Fermi level within the gap domain, the electrical conductance diverges at the ordering of graphene. Hence, we can conclude about the presence of a metal–dielectric transition. On the other hand, for a Fermi level occurring outside of the gap, we see an increase in the electrical conductance as a function of the order parameter. The analytic formulas obtained in the Lifshitz one-electron strong-coupling model, describing the one-electron states of graphene doped with substitutional impurity atoms in the limiting case of weak scattering, are compared to the results of numerical calculations. To determine the dependence of the energy spectrum and electrical conductance on the order parameter, we consider both the limiting case of weak scattering and the case of finite scattering potential. The contributions of the scattering of electrons on a vapor of atoms to the density of states and the electrical conductance of graphene with an admixture of interstitial atoms are studied within numerical methods. It is shown that an increase in the electrical conductance with the order parameter is a result of both the growth of the density of states at the Fermi level and the time of relaxation of electron states. We have demonstrated the presence of a domain of localized extrinsic states on the edges of the energy gap arising at the ordering of atoms of the admixture. If the Fermi level falls in the indicated spectral regions, the electrical conductance of graphene is significantly affected by the scattering of electrons on clusters of two or more atoms, and the approximation of coherent potential fails in this case.

Synthesis and properties of contorted hexabenzocoronenes with arylamino groups

Novel classes of contorted hexabenzocoronenes (c-HBCs) which exhibit a doubly concave configuration were synthesized by using hexabenzocoronene as bridge ligand and diphenylamine/triphenylamine as the redox-active termini. Although the analysis of the crystal structures of tri-di(4-methoxyphenyl)amino-substituted HBC (1), trimethoxy-substituted HBC (3) and tri(triphenylamine)-substituted HBC (4) show that the peripheral modified arylamine groups have a certain influence on the interaction force between molecules, the results of UV–vis absorption and fluorescence emission spectra indicate that these arylamine-modified hexabenzocoronenes have similar photophysical properties, which are primarily regulated by the c-HBC center. Subsequent electrochemical tests found that these compounds have multi-step redox process, and there is a certain degree of overlap between the arylamine and arylamine or between the arylamine and the bridge (c-HBC) during the oxidation process. Combining the UV-vis-NIR spectroelectrochemistry with the density functional theory (DFT) calculations, we further explored the electronic characters of the neutral and one-electron oxidation states of tri-di(4-methoxyphenyl)amino-substituted HBC (1), trimethoxy-substituted HBC (3) and tri(triphenylamine)-substituted HBC (4).

Mixed Basis Sets for Atomic Calculations

Many numerical methods of atomic calculations use one-electron basis sets. These basis sets must meet rather contradictory requirements. On the one hand, they must include physically justified orbitals, such as Dirac–Fock ones, for the one-electron states with high occupation numbers. On the other hand, they must ensure rapid convergence of the calculations in respect to the size of the basis set. It is difficult to meet these requirements using a single set of orbitals, while merging different subsets may lead to linear dependence and other problems. We suggest a simple unitary operator that allows such merging without aforementioned complications. We demonstrated robustness of the method on the examples of Fr and Au.

Concomitant Use of Tetrathiafulvalene and 7,7,8,8-Tetracyanoquinodimethane within the Skeletons of Metal-Organic Frameworks: Structures, Magnetism, and Electrochemistry.

In search of multifunctional metal-organic frameworks (MOFs), redox-active donors and acceptors, namely, tetrathiafulvalene (TTF) and 7,7,8,8-tetracyanoquinodimethane (TCNQ), were concomitantly used as skeletal components with diamagnetic metal nodes (Cd and Zn) to construct unique framework materials. Six isostructural frameworks were synthesized by diffusion of metal salts, TTF(py)4, and either paramagnetic Li(TCNQ) or diamagnetic H2TCNQ. They were characterized by single-crystal X-ray diffraction and FT-IR and UV-vis-NIR spectroscopy, and their physical properties were studied, including two postsynthetic modifications involving crystal-to-crystal transformations following a solid-solution reaction with I2. The highly colored crystals of two isostructural Zn and Cd frameworks contain undulating Cd-TTF(py)4 layers entwined with TCNQ in a chicken-wire net as part of the skeleton of the MOF as well as TCNQ intercalated within the channels, while nitrate anions are occluded within the cavities formed by the pyridine moieties. Reaction with I2 replaces each intercalated TCNQ•- within the channels with I3-. The optical properties and the electron paramagnetic resonance (EPR) spectra indicate the presence of only radical TCNQ•- in the parent compounds, while the magnetic susceptibilities enabled an estimation of the amount of TCNQ•- ( S = 1/2) leading to almost paramagnetic behavior. Solid-state electrochemistry provides evidence of several one-electron redox states corresponding to the electroactive cores.

Development of the Local (Site) Symmetry Method in the Supercell Model for a Crystal with an Impurity

Symmetry aspects of the periodic model of a crystal with a point defect (a supercell model or a extended unit cell (EUC) model) are considered; splitting of the Wyckoff positions in a primitive crystal cell with the introduction of supercell and the change of the one-electron states classification over k-vector (Brillouin zone folding) are discussed. When considering a point defect in a crystal in the supercell model, it is necessary to take into account the symmetry of the one-electron states of the original crystal at the top of the valence band and at the bottom of the conduction band. The selected supercell should reproduce these states. Each specific selection of a supercell corresponds to a specific splitting of the Wyckoff positions of the original crystal and, as a result, the possibility to place a defect in positions with different point symmetry and to perform a calculation without taking into account the point symmetry of the crystal with a defect at all (site symmetry method). By the results of the calculation of a crystal with a defect in the supercell model, taking into account site symmetry, it is possible to determine the real symmetry of the crystal with a defect, which is essential for the interpretation of experimental data. A copper impurity in a lithium node in a LiCl crystal retains the cubic symmetry of the atom being replaced; the impurity of an iron atom in a titanium site with cubic local symmetry in a SrTiO3 crystal lowers the symmetry to tetragonal; and the H site in the CsPbI3 crystal is characterized by the complete removal of point symmetry with the formation of an $${\text{I}}_{2}^{ - }$$ ion.

Graphene: Free electron scattering within an inverted honeycomb lattice

Theoretical progress in graphene physics has largely relied on the application of a simple nearest-neighbor tight-binding model capable of predicting many of the electronic properties of this material. However, important features that include electron-hole asymmetry and the detailed electronic bands of basic graphene nanostructures (e.g., nanoribbons with different edge terminations) are beyond the capability of such simple model. Here we show that a similarly simple plane-wave solution for the one-electron states of an atom-based two-dimensional potential landscape, defined by a single fitting parameter (the scattering potential), performs better than the standard tight-binding model, and levels to density-functional theory in correctly reproducing the detailed band structure of a variety of graphene nanostructures. In particular, our approach identifies the three hierarchies of nonmetallic armchair nanoribbons, as well as the doubly-degenerate flat bands of free-standing zigzag nanoribbons with their energy splitting produced by symmetry breaking. The present simple plane-wave approach holds great potential for gaining insight into the electronic states and the electro-optical properties of graphene nanostructures and other two-dimensional materials with intact or gapped Dirac-like dispersions.

Развитие метода локальной симметрии в модели суперъячейки для кристалла с примесью

The symmetry aspects of the supercell (extended primitive unit cell) model of the crystal with point defect are considered: Wyckoff positions splitting and the change of the one-electron states classification over k-vector (Brillouin zone folding). The supercell choice has to be made in a such a way that the one-electron states at the valence band top and the conduction band bottom for the perfect crystal are reproduced. Wyckoff positions splitting in the supercell model allows one to consider the defective crystal using different site symmetry point groups and also without use of the point symmetry at all. The site symmetry method allows one to predict the real symmetry of the defective crystal. This is demonstrated in the calculations of Cu impurity in LiCl crystal (the cubic symmetry of the perfect crystal is maintained for defective crystal), Fe impurity in SrTiO3 crystal (the point defect lowers the symmetry from cubic to tetragonal) and interstitial iodine atom in CsPbI3 crystal (the experimentally found I_2^- dumbell structure is confirmed only in the calculations without point symmetry restriction).

Entanglement and entropy in electron–electron scattering

Treating Coulomb scattering of two free electrons in a stationary approach, we explore the momentum and spin entanglement created by the interaction. We show that a particular discretisation provides an estimate of the von Neumann entropy of the one-electron reduced density matrix from the experimentally accessible Shannon entropy.For spinless distinguishable electrons the entropy is sizeable at low energies, indicating strong momentum entanglement, and drops to almost zero at energies of the order of 10 keV when the azimuthal degree of freedom is integrated out, i.e. practically no entanglement and almost pure one-electron states. If spin is taken into account, the entropy for electrons with antiparallel spins should be larger than in the parallel-spin case, since it embodies both momentum and spin entanglement. Surprisingly, this difference, as well as the deviation from the spin-less case, is extremely small for the complete scattering state. Strong spin entanglement can however be obtained by post-selecting states at scattering angle π/2.

G-Factor Calculation in Small Quantum Dots

It is shown that the effective Lande splitting factor or g-factor of electrons localized on heterostructures such as small quantum dots is always formed as a difference of two values. The first of themrelates to thematerial of the dot itself and critically depends on its sizes and shape; the second one relates to the barriermaterial (surrounding matrix); therewith, the dependence on the latter does not disappear at any dot sizes. The known (k, p) Kane theory defining the renormalization of electron mass and g-factor in bulk semiconductors, is modified for small quantum dots with “incomplete” band structure. Specific calculations of the electron ground state energy and g-factor are performed for the covariant InAs/AlSb heterostructure not localizing holes and, hence, capable of forming pure one-electron states (prototypes of solid-state qubits).

Halogen Photoelimination from SbV Dihalide Corroles.

Main-group p-block metals are ideally suited for mediating two-electron reactions because they cycle between M n and M n+2 redox states, as the one-electron state is thermodynamically unstable. Here, we report the synthesis and structure of an SbIII corrole and its SbVX2 (X = Cl, Br) congeners. SbIII sits above the corrole ring, whereas SbV resides in the corrole centroid. Electrochemistry suggests interconversion between the SbIII and SbVX2 species. TD-DFT calculations indicate a HOMO → LUMO+2 parentage for excited states in the Soret spectral region that have significant antibonding character with respect to the Sb-X fragment. The photochemistry of 2 and 3 in THF is consistent with the computational results, as steady-state photolysis at wavelengths coincident with the Soret absorption of SbVX2 corrole lead to its clean conversion to the SbIII corrole. This ability to photoactivate the Sb-X bond reflects the proclivity of the pnictogens to rely on the PnIII/V couple to drive the two-electron photochemistry of M-X bond activation, an essential transformation needed to develop HX-splitting cycles.

Thermal and magnetic properties of electron gas in toroidal quantum dot

One-electron states in a toroidal quantum dot in the presence of an external magnetic field have been considered. The magnetic field operator and the Schrodinger equation have been written in toroidal coordinates. The dependence of one-electron energy spectrum and wave function on the geometrical parameters of a toroidal quantum dot and magnetic field strength have been studied. The energy levels are employed to calculate the canonical partition function, which in its turn is used to obtain mean energy, heat capacity, entropy, magnetization, and susceptibility of noninteracting electron gas. The possibility to control the thermodynamic and magnetic properties of the noninteracting electron gas via changing the geometric parameters of the QD, magnetic field, and temperature, was demonstrated.