Width effects on bilayer graphene nanoribbon polarons.

Recent progress in nanoelectronics suggests that stacking armchair graphene nanoribbons (AGNRs) into bilayer systems can generate materials with emergent quasiparticle properties. In this context, the impact of width changes is especially relevant. However, its effect on charged carriers remains elusive. In this work, we investigate the effect of width and interlayer interaction changes on polaron states via a hybrid Hamiltonian that couples the electronic and lattice interactions. Results show the rising of two interlayer polarons: the non-symmetric and the symmetric. The coupling strength needed to induce the transition between states depends on the nanoribbon width, being at the most extreme case of ≈174 meV. Electronic properties such as the coupling strength threshold, carrier size, and gap are shown to respect the AGNR width family 3p, 3p + 1, and 3p + 2 rule. The findings demonstrate that strong interlayer interaction simultaneously delocalizes the carriers and reduces the gap up to 0.6 eV. Additionally, it is found that some layers are more prone to share charge, indicating a potential heterogeneous stacking where a particular electronic pathway is favored. The results present an encouraging prospect for integrating AGNR bilayers in future flexible electronics.

Magnetism and perfect spin filtering in pristine MgCl2 nanoribbons modulated by edge modification.

The search for new materials, with ideal electronic and magnetic properties for potential applications in nanoelectronics, has been extremely successful so far, and has paved the way for us to reimagine all technological devices. In the present work, we study the design of MgCl2 nanoribbons for applications in nanoelectronics and spintronics, by employing first-principles calculations based on density functional theory (DFT) and non-equilibrium Greens function techniques. Our results show that the properties of MgCl2 nanoribbons depend strongly not only on their geometrical form (armchair or zigzag) but also on the atoms at their edges. The armchair MgCl2 nanoribbon is a semiconductor and the zigzag nanoribbons vary from semiconducting, to metallic, to ferromagnetic, and to half-metallic, depending on the edge terminations. All these nanoribbons are very stable, with a relatively low cohesive energy per atom, and their attributes are not affected by the width of the nanoribbon. From transport calculations, we observed partial spin filtering in the ferromagnetic nanoribbon and perfect spin filtering in the two half-metallic nanoribbons. Moreover, we show how the current versus voltage curves can be fully understood by analysing the alignment of the energy levels of the electrodes. Our results corroborate the promising use of single-layer MgCl2 for the development of spintronics devices.

The van der Waals interactions in systems involving superheavy elements: the case of oganesson (Z = 118).

This work presents a study involving dimers composed of He, Ne, Ar, Kr, Xe, Rn, and Og noble gases with oganesson, a super-heavy closed-shell element (Z = 118). He-Og, Ne-Og, Ar-Og, Kr-Og, Xe-Og, Rn-Og, and Og-Og ground state electronic potential energy curves were calculated based on the 4-component (4c) Dirac-Coulomb Hamiltonian and were counterpoise corrected. For the 4c calculations, the electron correlation was taken into account using the same methodology (MP2-srLDA) and basis set quality (Dyall's acv3z and Dunning's aug-cc-PVTZ). All calculations included quantum electrodynamics effects at the Gaunt interaction level. For all the aforementioned dimers the vibration energies, spectroscopic constants (ωe, ωexe, ωeye, αe, and γe), and lifetime as a function of the temperature (which ranged from 200 to 500 K) were also calculated. The obtained results suggest that the inclusion of quantum electrodynamics effects reduces the value of the dissociation energy of all hetero-nuclear molecules with a percentage contribution ranging from 0.48% (for the He-Og dimer) to 9.63% (for the Rn-Og dimer). The lifetime calculations indicate that the Og-He dimer is close to the edge of instability and that Ng-Og dimers are relatively less stable when the Gaunt correction is considered. Exploiting scaling laws that adopt the polarizability of involved partners as scaling factors, it has also been demonstrated that in such systems the interaction is of van der Waals nature (size repulsion plus dispersion attraction) and this permitted an estimation of dissociation energy and equilibrium distance in the Og-Og dimer. This further information has been exploited to evaluate the rovibrational levels in this symmetric dimer and to cast light on the macroscopic properties of condensed phases concerning the complete noble gas family, emphasizing some anomalies of Og.

A Detailed Study of Electronic and Dynamic Properties of Noble Gas-Oxygen Molecule Adducts.

In this work, the binding features of adducts formed by a noble gas (Ng = He, Ne, Ar, Kr, Xe, and Rn) atom and the oxygen molecule (O2) in its ground Σg-3, in the past target of several experimental studies, have been characterized under different theoretical points of view to clarify fundamental aspects of the intermolecular bond. For the most stable configuration of all Ng-O2 systems, binding energy has been calculated at the theory's CCSD(T)/aug-cc-pVTZ level and compared with the experimental findings. Rovibrational energies, spectroscopic constants, and lifetime as a function of temperature were also evaluated by adopting properly formulated potential energy curves. The nature of the interaction involved was deeply investigated using charge displacement analysis, symmetry-adapted perturbation theory (SAPT), and natural bond orbital (NBO) methods. In all adducts, it was found that the charge transfer plays a minor role, although O2 is an open shell species exhibiting a positive electron affinity. Obtained results also indicate that the dispersion attraction contribution is the main responsible for the complex stability.

A Spectroscopic Validation of the Improved Lennard-Jones Model.

The Lennard-Jones (LJ) and Improved Lennard-Jones (ILJ) potential models have been deeply tested on the most accurate CCSD(T)/CBS electronic energies calculated for some weakly bound prototype systems. These results are important to plan the correct application of such models to systems at increasing complexity. CCSD(T)/CBS ground state electronic energies were determined for 21 diatomic systems composed by the combination of the noble gas atoms. These potentials were employed to calculate the rovibrational spectroscopic constants, and the results show that for 20 of the 21 pairs the ILJ predictions agree more effectively with the experimental data than those of the LJ model. The CCSD(T)/CBS energies were also used to determine the ß parameter of the ILJ form, related to the softness/hardness of the interacting partners and controlling the shape of the potential well. This information supports the experimental finding that suggests the adoption of ß≈9 for most of the systems involving noble gas atoms. The He-Ne and He-Ar molecules have a lifetime of less than 1ps in the 200-500 K temperature range, indicating that they are not considered stable under thermal conditions of gaseous bulks. Furthermore, the controversy concerning the presence of a "virtual" or a "real" vibrational state in the He2 molecule is discussed.

Polaron Properties in Armchair Graphene Nanoribbons.

By means of a 2-D tight-binding model with lattice relaxation in a first-order expansion, we report different polaron properties depending on the armchair graphene nanoribbons width family as well as on its size. We find that representatives of the 3p+2 family do not present a polaronic-mediated charge transport. As for 3p and 3p+1 families, the polaron behavior was completely dependent on the system's width. In particular, we observed a greater degree of delocalization for broader nanoribbons; narrower nanoribbons of both families, on the contrary, typically presented a more localized polaronic-type transport. Energy levels and occupation numbers analysis are performed to rigorously assess the nature of the charge carrier. Time evolution in the scope of the Ehrenfest molecular dynamics was also carried out to confirm the collective behavior and stability of the carrier as a function of time. We were able to determine that polarons in nanoribbons of 3p family present higher mobility than those in 3p+1 nanoribbons. These results identify the transport process that takes place for each system, and they allow the prediction of the mobility of the charge carriers as a function of the structural properties of the system, thus providing guidance on how to improve the efficiency of graphene nanoribbon-based devices.

Impact of the Electron-Phonon Interactions on the Polaron Dynamics in Graphene Nanoribbons.

The influence of the electron-phonon (e-ph) interactions on the filed-included polaron dynamics in armchair graphene nanoribbons (GNRs) is theoretically investigated in the scope of a two-dimensional tight-binding model. The results show that the localization of the polaronic charge increases when the strength of e-ph coupling also increases. Consequently, the polaron saturation velocity decreases for higher e-ph coupling strengths. Interestingly, the interplay between the e-ph coupling strength and the GNR width changes substantially the polaron dynamics properties.

Coupled-cluster based basis sets for valence correlation calculations.

Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via ⟨r(n)⟩ (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.

Concentration effects on intrachain polaron recombination in conjugated polymers.

The influence of different charge carrier concentrations on the recombination dynamics between oppositely charged polarons is numerically investigated using a modified version of the Su-Schrieffer-Heeger (SSH) model that includes an external electric field and electron-electron interactions. Our findings show that the external electric field can play the role of avoiding the formation of excited states (polaron-exciton and neutral excitation) leading the system to a dimerized lattice. Interestingly, depending on a suitable balance between the polaron concentration and the electric field strength, the recombination mechanism can form stable polaron-excitons or neutral excitations. These results may provide guidance to improve the electroluminescence efficiency in Polymer Light Emitting Diodes.

Critical temperature and products of intrachain polaron recombination in conjugated polymers.

The intrachain recombination dynamics between oppositely charged polarons is theoretically investigated through the use of a version of the Su-Schrieffer-Heeger (SSH) model modified to include an external electric field, an extended Hubbard model, Coulomb interactions, and temperature effects in the framework of a nonadiabatic evolution method. Our results indicate notable characteristics concerning the polaron recombination: (1) it is found that there exists a critical temperature regime, below which an exciton is formed directly and (2) a pristine lattice is the resulting product of the recombination process, if the temperature is higher than the critical value. Additionally, it is found that the critical electric field regime plays the role of drastically modifying the system dynamics. These facts suggest that thermal effects in the intrachain recombination of polarons are crucial for the understanding of electroluminescence in optoelectronic devices, such as Polymer Light Emitting Diodes.

Relativistic four-component potential energy curves for the lowest 23 covalent states of molecular bromine (Br2).

The covalent excited states and ground state of the Br2 molecule has been investigated by using four-component relativistic COSCI and MRCISD methods. These methods were performed for all covalent states in the representation Ω((±)). Calculated potential energy curves (PECs) were obtained at the four-component COSCI level, and spectroscopic constants (R(e), D(e), D0, ω(e), ω(e)x(e), ω(e)y(e), B(e), α(e), γ(e), Te, Dv) for bounded states are reported. The vertical excitations for all covalent states are reported at COSCI, MRCISD, and MRCISD+Q levels. We also present spectroscopic constants for two weakly bounded states (A':(1)2u and B':(1)0(-)u) not yet reported in the literature, as well as accurate analytical curves for all five relativistic molecular bounded sates [the ground state X:0 g(+) and the excited states A:(1)1(u), B:(1)0(u)(+), C:(2)1(u), and B':(1)0(u)(-)] found in this work.

In Silico Comparative Analysis of Ivermectin and Nirmatrelvir Inhibitors Interacting with the SARS-CoV-2 Main Protease.

Exploring therapeutic options is crucial in the ongoing COVID-19 pandemic caused by SARS-CoV-2. Nirmatrelvir, which is a potent inhibitor that targets the SARS-CoV-2 Mpro, shows promise as an antiviral treatment. Additionally, Ivermectin, which is a broad-spectrum antiparasitic drug, has demonstrated effectiveness against the virus in laboratory settings. However, its clinical implications are still debated. Using computational methods, such as molecular docking and 100 ns molecular dynamics simulations, we investigated how Nirmatrelvir and Ivermectin interacted with SARS-CoV-2 Mpro(A). Calculations using density functional theory were instrumental in elucidating the behavior of isolated molecules, primarily by analyzing the frontier molecular orbitals. Our analysis revealed distinct binding patterns: Nirmatrelvir formed strong interactions with amino acids, like MET49, MET165, HIS41, HIS163, HIS164, PHE140, CYS145, GLU166, and ASN142, showing stable binding, with a root-mean-square deviation (RMSD) of around 2.0 Å. On the other hand, Ivermectin interacted with THR237, THR239, LEU271, LEU272, and LEU287, displaying an RMSD of 1.87 Å, indicating enduring interactions. Both ligands stabilized Mpro(A), with Ivermectin showing stability and persistent interactions despite forming fewer hydrogen bonds. These findings offer detailed insights into how Nirmatrelvir and Ivermectin bind to the SARS-CoV-2 main protease, providing valuable information for potential therapeutic strategies against COVID-19.

Vibrational and electronic structure analysis of a carbon dioxide interaction with functionalized single-walled carbon nanotubes.

Electronic and vibrational properties of different single-walled carbon nanotubes (SWNTs) interacting with a CO2 molecule are investigated through the use of density functional theory (DFT) calculations and the discrete variable representation (DVR) method, respectively. We observed a considerable geometry difference between pristine and doped nanotubes. Consequently, a greater binding energy between the former type of nanotubes and the adsorbing molecule is achieved, a fact that finds experimental support and leads us to consider cobalt-doped nanotubes as promising candidates for chemical sensors. From the vibrational point of view, we note that the zigzag chirality tends to present higher values of vibrational frequencies for most of the states considered regardless of the nanotubes being doped or not. The potential energy curves (PECs) for the interactions between CO2 and all of the considered nanotubes together with spectroscopic constants are provided, and the reliability of the performed calculations makes the data a useful source of comparison for future works.

Impurity effects on polaron-exciton formation in conjugated polymers.

Combining the one-dimensional tight-binding Su-Schrieffer-Heeger model and the extended Hubbard model, the collision of two oppositely charged polarons is investigated under the influence of impurity effects using a non-adiabatic evolution method. Results show that electron-electron interactions have direct influence on the charge distribution coupled to the polaron-exciton lattice defect. Additionally, the presence of an impurity in the collisional process reduces the critical electric field for the polaron-exciton formation. In the small electric field regime, the impurity effects open three channels and are of fundamental importance to favor the polaron-exciton creation. The results indicate that the scattering between polarons in the presence of impurities can throw a new light on the description of electroluminescence in conjugated polymer systems.

Relativistic four-component MRCISD+Q calculations of the six lowest valence states of molecular [Formula: see text] anion including breit interactions.

CONTEXT AND RESULTS: This study aimed to obtain potential energy curves within a multireference 4-component relativistic method and to present spectroscopic constants (R[Formula: see text],[Formula: see text],[Formula: see text]x[Formula: see text],[Formula: see text]y[Formula: see text], D[Formula: see text], D[Formula: see text], B[Formula: see text],[Formula: see text],[Formula: see text],[Formula: see text] ), accurate extended Rydberg analytical form, and rovibrational levels for the 6 low-lying states of the I[Formula: see text] anion. For these states, some spectroscopic constants, rovibrational levels, and an accurate analytical form are presented for the first time in literature, and they are of interest for femtosecond and dynamics experiments of I[Formula: see text] as well as for electron attachment of I[Formula: see text]. This study suggests that the inclusion of relativistic and correlation effects treated at the MRCISD+Q level is needed to obtain reliable results, specially for D[Formula: see text]. COMPUTATIONAL AND THEORETICAL TECHNIQUES: The potential energy curves of the ground and the excited states of the molecular iodine anion (I[Formula: see text]) were investigated at multireference configuration interaction (MRCISD) with Davidson size-extensivity correction (denoted as +Q) within a fully relativistic four-component relativistic framework including Breit interaction.

Electronic and dynamical properties of non-covalent diatomic aggregates formed by He with neutral and ionic Li and Be.

CONTEXT AND RESULTS: This work aims to study the influence of the absence and presence of permanent charges on the electronic and dynamical properties of the non-covalent bound diatomic systems involving He and Li, Be as neutral and ionic partners. The charge displacement results suggest that in the formation of HeLi[Formula: see text], HeBe[Formula: see text], and HeBe[Formula: see text], the neutral He atom undergoes, in the electric field of the ion, a pronounced electronic polarization, and the natural bond order theoretical approach indicates that in the formation of the molecular orbital He acts as a weak electron donor. The energy decomposition analysis provides the dispersion and induction components as the attractive leading terms controlling the stability of all systems, confirming that the formed bond substantially maintains a non-covalent nature which is also supported by the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Finally, it was found that the HeLi and HeBe neutral systems are unstable under any condition, HeLi[Formula: see text] and HeBe[Formula: see text] ionic systems are stable below 317K and 138K, respectively, while the HeBe[Formula: see text] system becomes unstable only after 3045K. COMPUTATIONAL AND THEORETICAL TECHNIQUES: The potential energy curves and interactions in all systems were studied theoretically based on coupled-cluster singles and doubles method with perturbative inclusion of triples CCSD(T) method with an aug-cc-pV5Z basis set. More precisely, it was determined the potential energy curves describing the stability of the HeLi, HeLi[Formula: see text], HeBe, HeBe[Formula: see text], and HeBe[Formula: see text] systems, the charge displacement within the formed adducts, the decomposition of their total interaction energy, the topological analysis of their bonds, their rovibrational energies, their spectroscopic constants and lifetimes.

The H + Li2 bimolecular exchange reaction: dynamical and kinetical properties at J = 0.

For the first time in the literature, rigorous time-independent quantum scattering formalism was applied, by means of the ABC program, to the H + Li(2) → LiH + Li reaction. The state-to-state probabilities as a function of the total energy have been computed at zero total angular momentum (J = 0) allowing us to evaluate the effect of vibrational/rotational excitation on the reaction promotion/inhibition, the energetic distribution of products, and the temperature dependence of the J-shifting thermal rate coefficients.

Thermal rate constant calculation of the NF + F reactive system multiple arrangements.

In this work we analyzed the multiple channels of the reaction NF+F through the evaluation of thermal rate constants with both Wigner and Eckart tunneling corrections. Minimum energy paths and intrinsic reaction coordinates of the systems were obtained and accurately studied in order to ensure the consistency of our results. Specifically, we investigated the NF + F = N + F(2), NF + F = NF + F, and NF(2) = NF + F, reactive systems. As experimental data are available for the latter reaction, we were able to conclude that our thermal rate constants are in agreement for a wide range of temperatures. The here performed study is relevant to the understanding of the decomposition process of nitrogen trifluoride (NF(3)).

Exciton dissociation and charge carrier recombination processes in organic semiconductors.

Exciton dissociation and charge recombination processes in organic semiconductors, with thermal effects taken into account, are described in this paper. Here, we analyzed the mechanisms of polaron-excitons dissociation into free charge carriers and the consequent recombination of those carriers under thermal effects on two parallel π-conjugated polymers chains electronically coupled. Our results suggest that exciton dissociation in a single molecule give rise to localized, polaron-like charge carrier. Besides, we concluded that in the case of interchain processes, the bimolecular polaron recombination does not lead to an usual exciton state. Rather, this type of recombination leads to an oscillating dipole between the two chains. The recombination time obtained here for these processes are in agreement with the experimental results. Finally, our results show that temperature effects are essential to the relaxation process leading to polaron formation in a single chain, as in the absence of temperature, this process was not observed. In the case of two chains, we conclude that temperature effects also help the bimolecular recombination process, as observed experimentally.