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The magnesium hydride (MH)-doped carbon nanotubes (CNTs) are studied by density functional theory (DFT). MH is doped at three different sites of CNTs and the corresponding binding energies have been calculated. The hydrogen adsorption binding energies on these structures have been determined. The binding energy of adsorption for third and fourth H2molecule addition is exactly nearer to the applicable target, for achieving room temperature kinetics. The H site on CNT is the effective site for MH doping compared to other sites. The storage capacity of H2molecules, when five H2molecules are adsorbed on MH is 1.6wt%. It is shown that MH doped at various sites of CNT can be used as a good hydrogen storage medium at ambient temperatures. [ABSTRACT FROM PUBLISHER]

This Schiff base chemosensor (SNN) detected dual ions, Al 3+ and Zn 2+ ions selectively. Fluorescence spectrum investigations showed that Al 3+ ions increased fluorescence intensity, notably at 493 nm. Introducing Zn 2+ ions caused a significant blue shift of roughly ∼65 nm at a wavelength of 434 nm, resulting in a notable change in fluorescence intensity. When binding Al 3+ /Zn 2+ ions, the SNN receptor uses three methods. Inhibition of photoinduced electron transfer (PET), excited state intramolecular proton transfer (ESIPT), and restriction of CN isomerization. The jobs plot method found that SNN + Al 3+ and SNN + Zn 2+ complexations had a 1:1 stoichiometry. DFT, LC-HRMS, and 1 H NMR titration confirm this conclusion. The probe SNN's limit of detection (LOD) for Al 3+ /Zn 2+ ions was 3.99 nM and 1.33 nM. Latent fingerprint (LFP), food samples, pharmaceutical products, and E. coli pathogen bio-imaging have all used the SNN probe to identify Al 3+ and Zn 2+ ions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this computational study, we investigate the electronic properties of zigzag graphene nano-parallelograms (GNPs), which are parallelogram-shaped graphene nanoribbons of various widths and lengths, using thermally assisted occupation density functional theory (TAO-DFT). Our calculations revealed a monotonic decrease in the singlet-triplet energy gap as the GNP length increased. The GNPs possessed singlet ground states for all the cases examined. With the increase of GNP length, the vertical ionization potential and fundamental gap decreased monotonically, while the vertical electron affinity increased monotonically. Some of the GNPs studied were found to possess fundamental gaps in the range of 1-3 eV, lying in the ideal region relevant to solar energy applications. Besides, as the GNP length increased, the symmetrized von Neumann entropy increased monotonically, denoting an increase in the degree of the multi-reference character associated with the ground state GNPs. The occupation numbers and real-space representation of active orbitals indicated that there was a transition from the nonradical nature of the shorter GNPs to the increasing polyradical nature of the longer GNPs. In addition, the edge/corner localization of the active orbitals was found for the wider and longer GNPs.

For the ground-state properties of gas-phase nanomolecules with multi-reference character, thermally assisted occupation (TAO) density functional theory (DFT) has recently been found to outperform the widely used Kohn-Sham DFT when traditional exchange-correlation energy functionals are employed. Aiming to explore solvation effects on the ground-state properties of nanomolecules with multi-reference character at a minimal computational cost, we combined TAO-DFT with the PCM (polarizable continuum model). In order to show its usefulness, TAO-DFT-based PCM (TAO-PCM) was used to predict the electronic properties of linear acenes in three different solvents (toluene, chlorobenzene, and water). According to TAO-PCM, in the presence of these solvents, the smaller acenes should have nonradical character, and the larger ones should have increasing polyradical character, revealing striking similarities to the past findings in the gas phase.

Accurate prediction of properties of large-scale multi-reference (MR) electronic systems remains difficult for traditional computational methods (e.g., the Hartree-Fock theory and Kohn-Sham density functional theory (DFT)). Recently, thermally-assisted-occupation (TAO)-DFT has been demonstrated to offer reliable description of electronic properties of various large-scale MR electronic systems. Consequently, in this work, TAO-DFT is used to unlock the electronic properties associated with C-Belt[ n ] (i.e., the carbon nanobelts containing n fused 12-membered carbon rings). Our calculations show that for all the system sizes reported ( n = 4-24), C-Belt[ n ] have singlet ground states. In general, the larger the size of C-Belt[ n ], the more pronounced the MR character of ground-state C-Belt[ n ], as evident from the symmetrized von Neumann entropy and the occupation numbers of active TAO-orbitals. Furthermore, the active TAO-orbitals are delocalized along the circumference of C-Belt[ n ], as evident from the visualization of active TAO-orbitals.

It has been challenging to adequately investigate the properties of nanosystems with radical nature using conventional electronic structure methods. We address this challenge by calculating the electronic properties of linear carbon chains (l-CC[n]) and cyclic carbon chains (c-CC[n]) with n = 10-100 carbon atoms, using thermally-assisted-occupation density functional theory (TAO-DFT). For all the cases investigated, l-CC[n]/c-CC[n] are ground-state singlets, and c-CC[n] are energetically more stable than l-CC[n]. The electronic properties of l-CC[n]/c-CC[n] reveal certain oscillation patterns for smaller n, followed by monotonic changes for larger n. For the smaller carbon chains, odd-numbered l-CC[n] are more stable than the adjacent even-numbered ones; c-CC[[Formula: see text]]/c-CC[4m] are more/less stable than the adjacent odd-numbered ones, where m are positive integers. As n increases, l-CC[n]/c-CC[n] possess increasing polyradical nature in their ground states, where the active orbitals are delocalized over the entire length of l-CC[n] or the whole circumference of c-CC[n].

At the nanoscale, it has been rather troublesome to properly explore the properties associated with electronic systems exhibiting a radical nature using traditional electronic structure methods. Graphene nanoflakes, which are graphene nanostructures of different shapes and sizes, are typical examples. Recently, TAO-DFT (i.e., thermally-assisted-occupation density functional theory) has been formulated to tackle such challenging problems. As a result, we adopt TAO-DFT to explore the electronic properties associated with diamond-shaped graphene nanoflakes with n = 2-15 benzenoid rings fused together at each side, designated as n -pyrenes (as they could be expanded from pyrene). For all the n values considered, n -pyrenes are ground-state singlets. With increasing the size of n -pyrene, the singlet-triplet energy gap, vertical ionization potential, and fundamental gap monotonically decrease, while the vertical electron affinity and symmetrized von Neumann entropy (which is a quantitative measure of radical nature) monotonically increase. When n increases, there is a smooth transition from the nonradical character of the smaller n -pyrenes to the increasing polyradical nature of the larger n -pyrenes. Furthermore, the latter is shown to be related to the increasing concentration of active orbitals on the zigzag edges of the larger n -pyrenes.

It remains rather difficult for traditional computational methods to reliably predict the properties of nanosystems, especially for those possessing pronounced radical character. Accordingly, in this work, we adopt the recently formulated thermally-assisted-occupation density functional theory (TAO-DFT) to study two-atom-wide linear boron nanoribbons l-BNR[2,n] and two-atom-wide cyclic boron nanoribbons c-BNR[2,n], which exhibit polyradical character when the n value (i.e., the number of boron atoms along the length of l-BNR[2,n] or the circumference of c-BNR[2,n]) is considerably large. We calculate various electronic properties associated with l-BNR[2,n] and c-BNR[2,n], with n ranging from 6 to 100. Our results show that l-BNR[2,n] and c-BNR[2,n] have singlet ground states for all the n values examined. The electronic properties of c-BNR[2,n] exhibit more pronounced oscillatory patterns than those of l-BNR[2,n] when n is small, and converge to the respective properties of l-BNR[2,n] when n is sufficiently large. The larger the n values, the stronger the static correlation effects that originate from the polyradical nature of these ribbons. Besides, the active orbitals are found to be delocalized along the length of l-BNR[2,n] or the circumference of c-BNR[2,n]. The analysis of the size-dependent electronic properties indicates that l-BNR[2,n] and c-BNR[2,n] can be promising for nanoelectronic devices.

It has been extremely difficult for conventional computational approaches to reliably predict the properties of multi-reference systems (i.e., systems possessing radical character) at the nanoscale. To resolve this, we employ thermally-assisted-occupation density functional theory (TAO-DFT) to predict the electronic and hydrogen storage properties of Li-terminated linear boron chains (Li 2 B n ), with n boron atoms (n = 6, 8, …, and 16). From our TAO-DFT results, Li 2 B n , which possess radical character, can bind up to 4 H 2 molecules per Li, with the binding energies in the desirable regime (between 20 and 40 kJ/mol per H 2 ). The hydrogen gravimetric storage capacities of Li 2 B n range from 7.9 to 17.0 wt%, achieving the ultimate goal of the United States Department of Energy. Accordingly, Li 2 B n could be promising media for storing and releasing H 2 at temperatures much higher than the boiling point of liquid nitrogen.

Accurate prediction of the electronic and hydrogen storage properties of linear carbon chains (C n ) and Li-terminated linear carbon chains (Li 2 C n ), with n carbon atoms (n = 5-10), has been very challenging for traditional electronic structure methods, due to the presence of strong static correlation effects. To meet the challenge, we study these properties using our newly developed thermally-assisted-occupation density functional theory (TAO-DFT), a very efficient electronic structure method for the study of large systems with strong static correlation effects. Owing to the alteration of the reactivity of C n and Li 2 C n with n, odd-even oscillations in their electronic properties are found. In contrast to C n , the binding energies of H 2 molecules on Li 2 C n are in (or close to) the ideal binding energy range (about 20 to 40 kJ/mol per H 2 ). In addition, the H 2 gravimetric storage capacities of Li 2 C n are in the range of 10.7 to 17.9 wt%, satisfying the United States Department of Energy (USDOE) ultimate target of 7.5 wt%. On the basis of our results, Li 2 C n can be high-capacity hydrogen storage materials that can uptake and release hydrogen at temperatures well above the easily achieved temperature of liquid nitrogen.

Due to the presence of strong static correlation effects and noncovalent interactions, accurate prediction of the electronic and hydrogen storage properties of Li-adsorbed acenes with n linearly fused benzene rings (n = 3-8) has been very challenging for conventional electronic structure methods. To meet the challenge, we study these properties using our recently developed thermally-assisted-occupation density functional theory (TAO-DFT) with dispersion corrections. In contrast to pure acenes, the binding energies of H2 molecules on Li-adsorbed acenes are in the ideal binding energy range (about 20 to 40 kJ/mol per H2). Besides, the H2 gravimetric storage capacities of Li-adsorbed acenes are in the range of 9.9 to 10.7 wt%, satisfying the United States Department of Energy (USDOE) ultimate target of 7.5 wt%. On the basis of our results, Li-adsorbed acenes can be high-capacity hydrogen storage materials for reversible hydrogen uptake and release at ambient conditions.