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[Display omitted] • We studied heteronuclear fullerene nanocages (Al 12 N 12 , Al 12 P 12 , B 12 N 12 and B 12 P 12) for the separation and permeation of hydrogen isotopes. • Energy barrier for H+, D+, and T+ permeation through nanocages is computed. • Selectivity of proton isotopes through these nanocages is calculated by using zero-point energy (ZPE) difference of protium ion to its isotopes. To resolve the problem of mobile electrolytes for the permeation of hydrogen isotopes in fuel cells, we have studied herein heteronuclear fullerene nanocages (Al 12 N 12 , Al 12 P 12 , B 12 N 12 , and B 12 P 12) for the separation and permeation of hydrogen isotopes. The separation and permeation of fullerene nanocages for hydrogen isotopes are studied at ωB97XD functional of DFT along with 6–31g (d,p) pople basis set. Zero-point energy (ZPE) is calculated for Protium (H+) and its heavier isotopes including deuterium (D+) and tritium (T+). The Arrhenius equation is employed to calculate the selectivity of protium to deuterium (H+/D+) and deuterium to tritium (H+/T+) isotopes. The selectivity is calculated by using the zero-point energy difference (ZPE) of protium (H+) to its heavier isotopes. The proposed fullerene nanocages estimated better selectivity for proton isotopes. The phosphide-based nanocages (Al 12 P 12 , B 12 P 12) provide superior selectivity values of H+/D+ and H+/T+ compared to nitrogen-based nanocages (Al 12 N 12 , B 12 N 12). This study provides insights into separation pathways for proton isotopes through nanocages for many industrial applications in the energy sector. [ABSTRACT FROM AUTHOR]

[Display omitted] • The drug carrier ability of B 3 O 3 toward Foscarnet is investigated via DFT. • The interaction is characterized by the geometric, energetic, electronic, and optical analyses. • Widely accepted ωB97XD/6-31+G(d,p) method of DFT is adopted for geometric analysis whereas for electronic properties B3LYP/6-31+G (d,p) method is used. • NCI and QTAIM analyses confirmed the nature of interactions. In this study, B 3 O 3 quantum dot is investigated via density functional theory (DFT) calculations as an antiviral drug carrier toward Foscarnet. Geometric analysis is carried out to find stable orientations of interaction between Foscarnet drug and the B 3 O 3 quantum dot. As a result, three stable orientations are proposed. The E int of the most stable orientation is –32.63 kcal/mol whereas the BSSE corrected energy is −26.98 kcal/mol. Noncovalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses are employed to understand the nature and the type of interactions taking place between drug and the B 3 O 3 quantum dot. Their results indicated the presence of hydrogen bonding in the most stable complex (orientation A). The HOMO-LUMO analysis is performed to study the electronic properties of the interacting moieties. The lowest E gap is observed in case of orientation A. The value of dipole moments and chemical descriptors showed the significant activity of B 3 O 3 quantum dot toward Foscarnet drug molecule. The overall findings from this study suggest the B 3 O 3 quantum dot as a potential drug carrier system for antiviral drugs. [ABSTRACT FROM AUTHOR]

[Display omitted] • The adsorption of hazardous CH 3 X (X = F, Cl & Br) molecules on C 4 H 4 NH, C 4 H 4 O, C 4 H 4 S and C 6 H 6 monomer units has been studied. • The adsorption behaviors are evaluated by the geometric conformations, adsorption energies, SAPT and QTAIM topological analyses. • The effect of fluorination on the adsorption behavior is quantified. • The increase in adsorption strength is observed for the fluorinated adsorbents. Despite the numerous publications describing the synthesis and electronic properties of fluorinated furan, thiophene and pyrrole, the systematic overview of their adsorption applications is still lacking. In this study, the effect of fluorination on the adsorption properties of furan (C 4 H 4 O), thiophene (C 4 H 4 S), pyrrole (C 4 H 4 NH) and benzene (C 6 H 6) are investigated with the help of density functional theory (DFT) calculations. Herein, the adsorption energies of CH 3 X (X = F, Cl & Br) on C 4 H 4 O, C 4 H 4 S, C 4 H 4 NH and C 6 H 6 and their fluorinated analogues are calculated using ωB97XD/6-31+G(d, p) level of theory. The results of the adsorption energies and symmetry adapted perturbation theory (SAPT0) reveal that the adsorption affinity of adsorbent is enhanced upon fluorination due to the increasing dispersion forces. To comprehensively investigate the variation in the electronic properties of nonfluorinated and fluorinated systems, the HOMO, LUMO orbitals and NBO charges are analyzed. The isosurfaces of orbitals show that the electron density is more localized onto the fluorinated adsorbents which are probably due to the presence of multiple electronegative fluorine atoms. Owing to the electron-withdrawing nature of fluorine, the electronic charges are transferred from CH 3 X to fluorinated adsorbents while the charges are shifted from nonfluorinated adsorbents to CH 3 X. Furthermore, the TD-DFT calculations reveal that the electronic transition energies are significantly decreased in most of the fluorinated complexes especially, CH 3 X@C 4 F 4 S and CH 3 X@C 4 F 4 NH. With these findings, it can be postulated that fluorine substitution can significantly surge the electronic and adsorption properties of sensor materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • This study theoretically presents the sensing affinities of cyclic tetrapyrrole (CTPy) towards toxic gaseous molecules. • The sensitivity of CTPy is measured against the toxic chemicals namely NH 3 , NF 3 , NCl 3 and NBr 3. • ωB97XD/6-31+G(d, p) level of DFT has implemented to measure the sensitivity of CTPy. • DFT results proved that CTPy is highly sensitive towards the considered analytes. Toxic gas sensors with ultrahigh sensitivity are highly desirable and those can be achieved with the help of infinite π-conjugation of cyclic conducting polymers. In this DFT study, we demonstrate the adsorption performance of tetracyclic oligopyrrole (CTPy) towards NH 3 and nitrogen halides including NF 3 , NCl 3 and NBr 3. The CTPy possesses infinite conjugation and highly active cavity which provides an excellent platform for the adsorption of upcoming gas molecules. Thermodynamically, the observed interaction energies of NH 3 , NF 3 , NCl 3 and NBr 3 analytes with CTPy at ωB97XD/6-31+G(d,p) level of theory are −13.14, −3.00, −6.00 and −7.50 kcal/mol, respectively. In addition, the molecular dynamic simulations are performed at GFN2-xTB method to confirm the stability of CTPy and respective complexes. The SAPT0 and NCI analyses reveal that dispersion forces play a significant role to stablize these complexes. Moreover, the electrostatic component also contributes in stabilizing the NH 3 @CTPy, NCl 3 @CTPy and NBr 3 @CTPy complexes. The variation in the electronic properties including HOMO-LUMO gaps of complexes along with the significant NBO charge transfer indicate the increasing conductivity of CTPy upon complexation with reported analytes. The prominent charge transfer on interaction might be due to the increasing π to π* transition, thus the λ max is shifted to longer wavelength in UV–vis spectra. [ABSTRACT FROM AUTHOR]