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The emergence of hydrogen storage materials has drawn a lot of insurmountable attention in the scientific community due to the burgeoning demand for energy. As hydrogen not only performs well in various processes but can also be used as a source of alternative energy when paired with a cell technology like a fuel cell, it has gained increased significance. Herein, efforts are being undertaken to create effective hydrogen storage materials based on Ca 12 O 12 nanocages that have been endohedrally encapsulated with transition metals (TMs) (zinc, cadmium, and mercury). The synthesis of endohedrally doped Ca 12 O 12 is a complex process that involves solid-state reaction and diffusion of the modelled dopant atoms (zinc, cadmium, and mercury) into the internal cage. Thus, DFT calculations herein provide valuable insights into the underlying mechanisms and properties of the resulting doped materials. For all the systems under study, quantum chemical calculations were carried out using density functional theory (DFT) and time-dependent DFT at the PBE0/def2SVP level of theory. The adsorption energies of 10H 2 @ Ca 12 O 12 , 10H 2 @ZndopCa 12 O 12 , 10H 2 @CddopCa 12 O 12 , and 10H 2 @HgdopCa 12 O 12 systems were obtained in the range of −34.47 to 130.86 kcal/mol respectively and portrayed the efficient adsorption of H 2 on the metal-encapsulated systems. Also, considerable stabilization of the systems was obtained with higher charge separation which evidently correlates with the adsorption energy parametric values. Strong hydrogen bond and van der waals interaction was observed as the dominant interactions with a considerable binding energy of −9.72 kcal/mol. The proposed designed H 2 -adsorbed metal-encapsulated Ca 12 O 12 systems are effective systems for designing time-ahead hydrogen storage materials, according to the results of all investigations and global descriptions of reactivity. [Display omitted] • DFT study of metal doped Ca 12 O 12 for hydrogen storage at PBE0/def2SVP method. • The adsorption energies portrayed the efficient adsorption of H 2 on the metal-encapsulated systems. • Strong hydrogen bond and van der waals interaction was observed as the dominant interactions. • Designed H 2 -adsorbed metal-encapsulated Ca 12 O 12 systems are effective systems. • The results of all investigations and global descriptions of reactivity. [ABSTRACT FROM AUTHOR]

A high concentration of trimethylamine (TMA) in the body can be converted to trimethylamine N-oxide (TMAO), which is a well-known proatherogenic substance capable of accelerating atherosclerosis disease in humans. Hence, there is a pressing need for the development of fast, accurate and reliable nanomaterials for the detection of TMA. In this study, the interaction of TMA with aluminium nitride nanotube (AlNNT) and gallium-doped aluminium nitride nanotube (AlNGaNT) was investigated using density functional theory at the M06-2X, B3LYP, ωB97XD at 6-311G(d)/6-31G(d) levels of theory. The results of the interaction energy between AlNGaNT and TMA for the 6-31G(d) increased remarkable in the order of M06-2X: −1.57 < B3LYP-D3:1.58 < ωB97XD: 1.89 kcal mol−1, while the 6-311G(d) showed higher interaction energy in the order of B3LYP-D3: −1.96 < M06-2X: −1.99 < ωB97XD: −2.03 kcal mol−1. Generally, the interaction of TMA with AlNNT and AlNGaNT increases the global reactivity parameter. From topological, a strong interaction was observed from −0.010 to −0.050 a.u. for signλ2(r)ρ(r) function and 0.000 to 0.00 to 0.400 for aRDG in TMA/AlNGaNT, where at signλ2(r)ρ(r) more scattered plot was observed between −0.050 to −0.020 a.u. While the small scattered plot was observed for TMA/AlNGaNT at 0.00 to −0.010 a.u. for signλ2(r)ρ(r) and aRDG of 0.00 to 0.400. Therefore, it was proposed that an electrostatic interaction is the mechanism between TMA and the AlNNC, and the strength of the interaction increase with the addition of Ga-atom as in AlNGaNT. [ABSTRACT FROM AUTHOR]

Applying density functional theory (DFT), an attempt has been made to investigate the intermolecular interactions between the serine amino acid and pristine boron nitride, Al-doped boron nitride, and carbon boron nitride nanotubes (BNNT, BNAlNT, and BC2NNT, respectively). One of the most suitable basis functionals for the systems studied in this research is 6-311G (d), which has been used in both optimization calculations and calculations related to wave function analyses. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital (NBO), non-covalent interactions (NCI), and quantum theory of atoms in molecules (QTAIM) were consistent and favored physical adsorption in all systems. Al-doped nanotube provides more adsorption energy than others. The HOMO–LUMO energy gaps were as follows: BNNT: 6.545, BNAlNT: 8.127, and BC2NNT: 7.027 eV at B3LYP-D3/6-311G (d) model chemistry. The adsorption sensitivity increased when an amino acid molecule interacted with doped BNNT and could be used to design a nanocarrier for serine amino acid. [ABSTRACT FROM AUTHOR]

Herein, the aim of this work was to investigate the intermolecular interactions between polyoxometalate (POMs) as a drug‐delivery system with nitrosourea at different sites: CH3, COOH, NH2, NO2 and OCH3 using density functional theory (DFT) at the M062X/LanL2DZ level of theory. The result showed that, the lowest bond lengths recorded for the adsorbate and the nanocage were 1.40Å, 1.64Å, 1.40Å and 1.57Å for NU/POM(CH3), NU/POM(NH2), NU/POM(NO2) and NU/POM(OCH3) respectively. The NU/POM(NO2) system had the highest adsorption energy in the three phases: −32.039, −26.95, and −29.38 kcal/mol for gas, solvent, and benzene respectively and the lowest was shown in NU/POM(OCH3) with −14.10, −10.33, −12.29 kcal/mol. The energy gap was found to be the highest in NU/POM(NO2) with 5.061eV followed by NU/POM and NU/POM(COOH) 4.020eV and 4.003eV respectively. It has been clearly shown that NU/POM(NO2) density peak in the Highest occupied molecular orbital and Lowest unoccupied molecular orbital (HOMO/LUMO) plot was above 5 and this go in line with the electronic properties possessing a stable nature. In the NBO analysis, after adsorption of the nitrosourea (NU), the NU/POM(NO2) system recorded the highest energy with 1309.42 kcal/mol and the lowest in NU/POM(OCH3) with 921.75 kcal/mol. The system with NO2 possess more stability, chemical hardness, electrophilicity index and strong interactions. It has a better surface interaction than other compounds found in Nitrosourea. [ABSTRACT FROM AUTHOR]

The study of intermolecular interactions is of great importance. This study attempted to quantitatively examine the interactions between Serine (C3H7NO3) and fullerene nanocages, C60, in vacuum. As the frequent introduction of elements as impurities into the structure of nanomaterials can increase the intensity of intermolecular interactions, nanocages doped with silicon and germanium have also been studied as adsorbents, C59Si and C59Ge. Quantum mechanical studies of such systems are possible in the density functional theory (DFT) framework. For this purpose, various functionals, such as B3LYP-D3, ωB97XD, and M062X, have been used. One of the most suitable basis functionals for the systems studied in this research is 6-311G (d), which has been used in both optimization calculations and calculations related to wave function analyses. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital, non-covalent interactions, and quantum theory of atoms in molecules were consistent and in favor of physical adsorption in all systems. Germanium had more adsorption energy than other dopants. The HOMO–LUMO energy gaps were as follows: C60: 5.996, C59Si: 5.309 and C59Ge: 5.188 eV at B3LYP-D3/6–311 G (d) model chemistry. The sensitivity of the adsorption increased when an amino acid molecule interacted with doped C60, and this capability could be used to design nanocarrier to detect Serine amino acid. [ABSTRACT FROM AUTHOR]

The study of intermolecular interactions is of great importance. This study attempted to quantitatively examine the interactions between acrolein (C3H4O) and fullerene nanocages, C60, in vacuum. As the frequent introduction of elements as impurities into the structure of nanomaterials can increase the intensity of intermolecular interactions, nanocages doped with silicon and germanium have also been studied as adsorbents, C59Si and C59Ge. Quantum mechanical studies of such systems are possible in the density functional theory (DFT) framework. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital, non-covalent interactions, and quantum theory of atoms in molecules were consistent and in favor of physical adsorption in all systems. Germanium had more adsorption energy than other dopants. The HOMO–LUMO energy gaps were as follows: C60: 5.996, C59Si: 5.309, and C59Ge: 5.188 eV at B3LYP-D3/6-311G (d) model chemistry. The sensitivity of the adsorption increased when a gas molecule interacted with doped C60, and this capability could be used to design nanosensors to detect acrolein gas. [ABSTRACT FROM AUTHOR]

We examined the gas sensing abilities of Li-decorated B 12 C 6 N 6 (B 12 C 6 N 6 Li) hybrid nanocage, introducing B 12 C 6 N 6 for the first time in sensing applications. The toxic gas molecules like Cl 2 , COCl 2 , H 2 S, and NH 3 were considered. The B 12 C 6 N 6 nanocage with C 2 V symmetry displayed the lowest energy among its isomers. Li exhibited stronger anchoring above B 3 C 2 N ring compared to B 2 C 2 , B 2 N 2 , and B 3 CN 2 rings of B 12 C 6 N 6 nanocage, displaying a binding energy of −3.30 eV. Li decoration resulted in asymmetric spin-up and spin-down states near Fermi level, indicating magnetic nature of complexes. B 12 C 6 N 6 , an electron-deficient nanocage, displayed charge transfer from Li atom to the nanocage. Substantial changes in electronic states occurred following the adsorption of Cl 2 and COCl 2 molecules. COCl 2 , H 2 S, and NH 3 adsorption is thermodynamically favourable over a wide temperature and pressure range, while Cl 2 adsorption is favourable only within a confined range. Earlier findings indicate dissociative adsorption of Cl 2 on nanocages rendering the substrate to be non-reusable. B 12 C 6 N 6 Li considered here is superior over other nanocages as Cl 2 adsorbs in molecular form while B 12 C 6 N 6 Li also demonstrates significant sensitivity. B 12 C 6 N 6 Li nanocage is unsuitable for sensing H 2 S and NH 3 gas molecules but holds promise as a potential candidate for sensing Cl 2 and COCl 2 gas molecules. [Display omitted] • B 12 C 6 N 6 Li is not suitable for NH 3 and H 2 S sensing. • B 12 C 6 N 6 Li shows promise as a potential candidate for sensing Cl 2 and COCl 2 • Li bound more strongly with B 3 C 2 N ring than other rings. • B 12 C 6 N 6 Li exhibits magnetic nature and a significant dipole moment. [ABSTRACT FROM AUTHOR]

The study of intermolecular interactions is of great importance. This study attempted to quantitatively examine the interactions between cysteine (C3H7NO2S) amino acid molecule with pristine boron nitride, Al-doped boron nitride and carbon boron nitride nanotubes (BNNT, BNAlNT, BC2NNT, respectively) in vacuum. Quantum mechanical studies of such systems are possible in the density functional theory (DFT) framework. For this purpose, various functionals, such as B3LYP-D3, ωB97XD and M062X, have been used. One of the most suitable basis functionals for the systems studied in this research is 6-311G(d), which has been used in both optimization calculations and calculations related to wavefunction analyses. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital, non-covalent interactions and quantum theory of atoms in molecules were consistent and in favour of physical adsorption in all systems. Al-doped nanotube provides more adsorption energy than others. The highest occupied molecular orbital and lowest unoccupied molecular orbital energy gaps were as follows: BNNT: 6.545, BNAlNT: 8.127 and BC2NNT: 7.027 eV at B3LYP-D3/6-311G(d) model chemistry. The sensitivity of the adsorption increased when an amino acid molecule interacted with doped BNNT, and could be used to design a nanocarrier for cysteine amino acid. [ABSTRACT FROM AUTHOR]

The study of intermolecular interactions is of great importance. This study attempted to quantitatively examine the interactions between bromine monochloride (BrCl) with pristine boron nitride nanotube (BNNT) armchair (5,5) and zigzag (7,0) as well as armchair (5,5) BC2NNT and zigzag (7,0) BC2NNT in vacuum. Quantum mechanical studies of such systems are possible in the density functional theory (DFT) framework. For this purpose, various functionals, such as B3LYP-D3, ω B97XD, and M062X, have been used. One of the most suitable basis functionals for the systems studied in this research is 6-311G (d), which has been used in both optimization calculations and calculations related to wave function analyses. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital, non-covalent interactions, and quantum theory of atoms in molecules (QTAIM) were consistent and in favor of physical adsorption in all systems. Gallium had more adsorption energy than other dopants. The HOMO–LUMO energy gaps were as follows: BNNT (5,5): 10.296, BNNT (7,0): 9.015, BC2NNT (5,5): 7.022, and BC2NNT (7,0): 5.979 eV at B3LYP-D3/6-311G (d) model chemistry. The strongest interaction is related to the BC2NNT (7,0)/BrCl cluster: − 0. 4 8 8 eV. The results of QTAIM and NCI analysis identified the intermolecular interactions of the type of strong van der Waals interaction for these nanotubes. The sensitivity of the adsorption increased when a gas molecule interacted with carbon-doped BNNT, and the change in the frontier orbital gap could be used to design nanosensors to detect BrCl gas. The interactions between BrCl with BNNT) armchair (5,5) and zigzag (7,0) as well as armchair (5,5) BC2NNT and zigzag (7,0) BC2NNT were studied. The sensitivity of the adsorption increased when the gas molecule interacted with carbon doped BNNT. The results of conceptual DFT, NBO, NCI, and QTAIM analyses were consistent and in favor of physical adsorption in all systems. [ABSTRACT FROM AUTHOR]

The study of intermolecular interactions is of great importance. This study attempted to quantitatively examine the interactions between cysteine (C3H7NO2S) and fullerene nanocages, C60, in vacuum. As the frequent introduction of elements as impurities into the structure of nanomaterials can increase the intensity of intermolecular interactions, nanocages doped with silicon and germanium have also been studied as adsorbents, C59Si and C59Ge. Quantum mechanical studies of such systems are possible in the density functional theory (DFT) framework. For this purpose, various functionals, such as B3LYP-D3, ωB97XD, and M062X, have been used. One of the most suitable basis functionals for the systems studied in this research is 6-311G (d), which has been used in both optimization calculations and calculations related to wave function analyses. The main part of this work is the study of various analyses that reveal the nature of the intermolecular interactions between the two components introduced above. The results of conceptual DFT, natural bond orbital, non-covalent interactions, and quantum theory of atoms in molecules were consistent and in favor of physical adsorption in all systems. Germanium had more adsorption energy than other dopants. The HOMO–LUMO energy gaps were as follows: C60: 5.996, C59Si: 5.309, and C59Ge: 5.188 eV at B3LYP-D3/6–311 G (d) model chemistry. The sensitivity of the adsorption increased when an amino acid molecule interacted with doped C60, and this capability could be used to design nanocarrier to carry cysteine amino acid. [ABSTRACT FROM AUTHOR]

[Display omitted] • DRTTBDT-A1: Remarkable characteristics suggest high performance in OSCs (3.84 eV gap, 519 nm λmax, 5.92 D dipole moment). • Enhanced operational efficiency: Higher V OC and PCE in newly designed molecules compared to the reference. • PCE values range from 27.90 to 31.71 among newly engineered molecules, surpassing the reference (27.49 PCE). • Structural modifications offer promise in designing proficient photovoltaic materials, advancing solar energy research. Four small molecule (DRTTBDT-A1 to DRTTBDT-A4) based on Benzodithiophene were studied for their optoelectronic properties and compared to the reference molecule (DRTTBDT-R) as potential donors in organic solar cells. The designed molecules feature electron-withdrawing moieties attached to both terminals of the reference molecule. Computational investigations using density functional theory indicated that DRTTBDT-A1 displayed the most intriguing characteristics in dichloromethane solvent, with a small energy gap of 3.84 eV, a high λ max at 519 nm, and a large dipole moment of 5.92 D. These features suggest superior miscibility and potential for high performance in OSCs. The newly engineered molecules also exhibited higher open-circuit voltage and power conversion efficiency compared to the reference, indicating enhanced operational efficiency. PCE values ranging from 27.90 to 31.71 were observed, surpassing the reference molecule's PCE of 27.49. These findings demonstrate the potential of structural modifications in designing efficient photovoltaic materials for solar energy applications. [ABSTRACT FROM AUTHOR]

In this investigation, the feasibility of detecting the amantadine (AMD) molecule onto the outer surface of pristine fullerene (C 6 0 ), as well as C 5 9 X (X = Si , Ge, B, Al, Ga, N, P, and As) decorated structures, was carefully evaluated. For achieving this goal, a density functional theory level of study using the HSEH1PBE functional together with a 6-311G(d) basis set has been used. Subsequently, the B3LYP-D3, wB97XD and M062X functionals with a 6-311G(d) basis set were also employed to consider the single point energies. Natural bond orbital (NBO) and the quantum theory of atoms in molecules (QTAIM) were implemented using the B3LYP-D3/6-311G(d) method and the results were compatible with the electronic properties. In this regard, the total density of states (TDOSs), the Wiberg bond index (WBI), natural charge, natural electron configuration, donor–acceptor NBO interactions, and the second-order perturbation energies are performed to explore the nature of the intermolecular interactions. All of the energy calculations and population analyses denote that by adsorbing of the AMD molecule onto the surface of the considered nanostructures, the intermolecular interactions are of the type of strong physical adsorption. Among the doped fullerenes, Ge-doped structure has very high adsorption energy compared to other elements. Generally, it was revealed that the sensitivity of the adsorption will be increased when the AMD molecule interacts with the decorated fullerenes and decrease the HOMO–LUMO band gap; therefore, the change of electronic properties can be used to design suitable nanocarrier. The feasibility of detecting the amantadine molecule onto the outer surface of pristine fullerene, as well as C59X (X = Si, Ge, B, Al, Ga, N, P, and As) decorated structures, was carefully evaluated. Various analyses such as the total density of states, the Wiberg bond order, natural bond orbital, noncovalent interaction, and quantum theory of atom in molecule were performed to shed light on the nature of intermolecular interactions. Results show that the change in electronic properties can be used to design suitable nanocarrier. [ABSTRACT FROM AUTHOR]

The feasibility of detecting a Chlorofluoromethane (CFM) gas molecule on the outer surface of a pristine single‐walled boron nitride nanotube as well as Al‐, Ga‐, P‐, and As‐doped structures. A periodic boundary condition (PBC), within a density functional theory (DFT) method, using the Perdew, Burke, and Ernzerhof exchange‐correlation (PBE0) functional, together with a 6‐311G(d) basis set was used. Subsequently, the B3LYP, CAM−B3LYP, ωB97XD, and M06‐2X functionals were also employed to consider the single point energies. Natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) were implemented by using the PBE0/6‐311G(d). To explore the nature of the intermolecular interactions, density of state (DOS), Wiberg bond index (WBI), natural charge, natural electron configuration, donor–acceptor natural bond orbital interactions, the second‐order perturbation energies tests, and noncovalent interaction (NCI) analysis are performed. The sensitivity of the adsorption will be increased when the gas molecule interacts with decorated nanotubes; therefore, the change of electronic properties can be used to design suitable nanosensors. [ABSTRACT FROM AUTHOR]

[Display omitted] • The interaction of VCM with BNNS, BNAlNS, and BNGaNS are studied. • To study the adsorption processes, the results of an NBO analysis are analyzed. • To unravel the nature of intermolecular interactions a QTAIM analysis is applied. • NCI analysis were performed to consider the non-covalent interactions. Utilizing density functional theory, an investigation was conducted to scrutinize the nature of interactions between the vinyl chloride and the pristine, Al-, and Ga-doped boron nitride nanosheets. A range of functionals, namely B3LYP-D3, PBE0, ωB97XD, and M06-2X, were meticulously selected for all structural configurations. Each functional was harmoniously coupled with the 6-311G(d) basis functions. In-depth analysis of the electronic sructure was accomplished through a comprehensive examination of the total density of state. Furthermore, the examination encompassed the application of quantum theory of atoms in molecules, natural bond orbitals, and non-covalent interaction approaches to elucidate the underlying nature of the gas-nanosheet interactions. Remarkably, the insertion of dopant atoms into the nanosheets resulted in a striking alteration of the location of the HOMO-LUMO energy gap. Among all the adsorbents, Ga-doped system emerged as the preeminent material, exhibiting superior potential for deployment in the creation of sensors or gas removal apparatuses. [ABSTRACT FROM AUTHOR]

The periodic boundary condition density functional theory framework was recruited in order to study the reactivity and electronic sensitivity of aluminium nitride (AlN) and silicon carbide (SiC) nanotubes as well as the gallium‐doped aluminium nitride (AlN(Ga)) and germanium‐doped silicon carbide (SiC(Ge)) nanotubes toward noble gases (NGs). In this respect, the adsorption possibility of the He, Ne, Ar, and Kr NGs onto the exterior surface of AlN, SiC, AlN(Ga) and SiC(Ge) nanotubes in the form of single‐walled armchair (5,5) was comprehensively and comparatively investigated. All possible configurations were considered and optimized at B3LYP/6‐311G (d) level of theory for each unit cells. Moreover, the single point energy calculations were applied on the completed nanotube/gas systems using different functionals including B3LYP, WB97X‐3D, M062X, and CAM−B3LYP in combination with 6–311G (d) and DEF2‐TZVP basis sets. It was found that, there are tiny differences between any possible configurations of gas and nanotube systems, and therefore, the most stable configuration of each system was chosen for further analyses such as density of state, natural bond orbital, and quantum theory of atoms in molecules in order to better understand the intermolecular interaction between NGs and nanotubes. The obtained results indicate that, the Ga‐doped and Ge‐doped nanotubes are more profound in the sensing of NGs compared to the pristine nanotubes. The feasibility of pristine AlN and SiC as well as decorated AlN(Ga) and SiC(Ge) single wall nanotubes in sensing of He, Ne, Ar and Kr noble gases was studied theoretically based on density functional theory methods. It was found that, the Ga‐doped AlN and Ge‐doped SiC nanotubes are more sensitive than pristine AlN and SiC nanotubes, and therefore, they are highly recommended for designing noble gas sensors. [ABSTRACT FROM AUTHOR]

[Display omitted] • Quantum analysis shows an enhanced efficiency of organic solar cells. • A4 molecule shows outstanding miscibility and high absorption. • All proposed chromophores exhibit high power conversion efficiency. • End-capped modifications positively impact optoelectronic properties. In this study, quantum chemical and density functional theory (DFT) methods were used to investigate triphenyldiamine-based molecules for enhancing organic solar cells (OSCs). A reference molecule (XSln84) [(E)-2′-methoxy-N4,N4,N4″,N4″-tetrakis(4-methoxyphenyl)-5′-(4-methoxystyryl)-[1,1′:3′,1″-terphenyl]-4,4″-diamine)] and six modified molecules (A1 to A6) were analyzed. The molecular properties of these molecules were thoroughly investigated, including maximum absorption wavelength (λmax), frontier molecular orbitals (FMO), and quantum chemical parameters. A4 showed excellent miscibility, highest absorption wavelength, small energy gap, and high dipole moment in dichloromethane DCM solvent. Compared to the reference molecule, all modified molecules exhibited higher estimated open-circuit voltage (V OC) and remarkable power conversion efficiency (PCE), with A5 having the highest PCE. A3 had the highest electron mobility, while A6 showed the highest hole mobility. The end-capped modifications improved the optoelectronic properties, suggesting potential for efficient OSCs. These findings contribute to understanding these molecules and their renewable energy applications, benefiting the field of organic solar cells. [ABSTRACT FROM AUTHOR]

A comparative study of doping of the first row transition metals (from Sc to Zn) onto all available adsorption sites of the exterior surface of B 12 N 12 nanocage has been performed by DFT method at B3LYP/def2-TZVP(-f) level of theory. The geometrical structures, electronic properties, population and quantum theory of atoms in molecules (QTAIM) analyses are also performed to better understand the cage/metal interactions. It can be inferred from results that nine metals from Sc to Cu tend to chemisorb onto B 12 N 12 nanocage via covalent interactions, where Zn metal physisorbed through weak Van der Waals interaction. Density of state analysis indicates that doped metal can modify significantly electronic properties of nanocage by decreasing HOMO-LUMO band gap and increasing metallic character. Besides, based on the maximum hardness and the minimum electrophilicity principles, it seems that the reactivity of the cage/metal clusters was increased compared to the pristine cage. It is also found that among the first row transition metals, Mn exhibits the strongest affinity toward B 12 N 12 nanocage with the most negative binding energy. [ABSTRACT FROM AUTHOR]

[Display omitted] • The energy of adsorption of the cluster has been calculated. • Weak interaction analysis has been performed. • QTIAM, NBO, and conceptual DFT considerations were employed to study the systems. • NCI analysis was performed to consider the non-covalent interactions. The density functional theory (DFT) framework was used to investigate the intermolecular interactions between cyanogen chloride (CNCl) pollutant gas molecule with pristine boron nitride nanotubes (BNNT), Al-doped boron nitride nanotubes (BNAlNT), and carbon boron nitride nanotubes (BC 2 NNT). The geometric structures of the resulting systems have been optimized using different methods, including B3LYP-D3(GD3BJ)/6-311G(d), ωB97XD/6-311G(d), and M06-2X/6-311G(d). The computed adsorption energies suggest that the studied nanotubes can enhance adsorption of CNCl, and thus promote its detection when employed as sensing materials. Wave function analysis has been implemented to study the type of intermolecular interactions at ωB97XD/6-311G(d,p) level of theory. Natural bond orbital (NBO) analysis has been used to study the charge transfer and bond order. Quantum theory of atoms in molecules (QTAIM) analysis has also been used to determine the type of interactions between the target gas and the nanotubes. To investigate the weak intermolecular interactions we also carried out non-covalent interaction analysis (NCI). The results also indicate that the CNCl-nanotube systems are created through physisorption as they are dominated by non-covalent interactions. The predicted adsorption energies increase as follows: BNAlNT: −1.175 eV > BC 2 NNT: −0.281 eV > BNNT: −0.256 eV; this shows that the aluminum-doped boron nitride nanotube is the best option from promoting adsorption of the target gas among them. The HOMO–LUMO energy gaps were as follows: BNNT: 7.090, BNAlNT: 9.193, and BC 2 NNT: 7.027 eV at B3LYP-D3/6-311G(d) level of theory. [ABSTRACT FROM AUTHOR]

This study reports interaction between toxic gas bromochlorodifluoromethane (BCF) and pristine and Al, Ga, P and As atom doped BN nanosheets (BNNS) using density functional theory with various functionals such as PBE0, B3LYP-D3, ωB97XD, and M06–2X with 6-311G(d) basis set. The pristine, Al, Ga, P and As doped nanosheets are denoted by BNNS, BNAlNS, BNGaNS, BNPNS, and BNAsNS respectively. Several descriptors are used to reveal the molecular interaction between the BCF and doped nanosheets. The results from density functional theory are confirmed using natural bond orbital analysis, non-covalent interactions, Quantum Theory of Atoms in Molecule (QTAIM) etc. which indicates physisorption of BCF on the pristine and doped nanosheets. Gallium doped BNNS shows higher adsorption energy for BCF than Al, P and As doped BNNS. The HOMO–LUMO energy gaps are found to be 5.729, 5.739, 5.742, 4.799, and 4.535 eV for BNNS, BNAlNS, BNGaNS, BNPNS, and BNAsNS, respectively at B3LYP-D3/6-311G(d) level indicating the stability of the structures. The sensitivity of the BCF adsorption has increased for doped BNNS than pristine BNNS. The doped BNNS can be used to design the BCF gas sensor. [Display omitted] • The interactions between Bromochlorodifluoromethane with BNNS were studied. • The sensitivity of the adsorption increased by doping Al, Ga, P, and As in the BNNS. • The results of conceptual DFT, NBO, NCI, and QTAIM analyses were widely discussed. [ABSTRACT FROM AUTHOR]

[Display omitted] • The adsorption of halomethanes onto X 12 Y 12 nanocages is studied. • Energy, geometry and the reactivity of cage/cluster systems are investigated. • NBO and QTAIM analysis results are analyzed to investigate the adsorption process. • To find out the nature of intermolecular interactions, a RDG diagrams are depicted. The feasibility of detecting halomethanes containing CH 3 F, CH 3 Cl, and CH 3 Br onto the exterior surface of inorganic-based nanocages X 12 Y 12 (X = B, Al, Ga, and Y = N, P, As) was investigated using a density functional theory (DFT). All of the configurations, including the pristine halomethanes or nanocages and the gas/nanocage systems, were optimized by B3LYP functional and DEF2-TZVP basis sets. Comparative single point energy calculations were performed using different functional containing B3LYP, M06-2X, ωB97XD, and CAM-B3LYP, together with DEF2-TZVP and DEF2-QZVP. Al 12 N 12 , Al 12 P 12 , Al 12 As 12 have relatively higher adsorption energies compared with other studied here. Cages with Boron viz. B 12 N 12 , B 12 P 12 , B 12 As 12 found to have very weak interaction with halomethanes. HOMO-LUMO gap and total density of states (TDOS) plots were analyzed to confirm the kind of interaction nanocages having with halomethanes. The nature of intermolecular interactions was considered by implementing the quantum theory of atoms in molecules (QTAIM). The adsorption of halomethanes onto nanocages was found to be exothermic and hence energetically favorable. [ABSTRACT FROM AUTHOR]

[Display omitted] • Adsorption of alkali and alkaline earth ions onto the surface of inorganic nanocages. • The results of an NBO and QTAIM analyses are analyzed. • To find out the nature of intermolecular interactions aRDG diagrams are depicted. The adsorption of alkali and alkaline earth ions onto the exterior surface of inorganic nanocages X 12 Y 12 (X = B, Al, Ga and Y = N, P, As) was investigated by using the density functional theory (DFT). All of the configurations, including the pristine ions or nanocages, as well as the ion adsorbed nanocage systems, were optimized using B3LYP-D3 functional and DEF2-TZVP basis sets. Comparative single point energy calculations were performed using different functionals viz. B3LYP-D3, M06-2X, ωB97XD and CAM-B3LYP, together with DEF2-TZVP and DEF2-QZVP basis sets. The results of natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM), and non-covalent interaction (NCI) analyses were compatible with the results of electronic properties. Total density of states (TDOSs), the natural charge, Wiberg bond index (WBI), natural electron configuration, donor–acceptor NBO interactions and second-order perturbation energies are obtained. Strong interaction between the ions and the nanocages is observed and the tendency of the ions to adsorb onto the surfaces of the mentioned X 12 Y 12 nanocages is in the order Be++ > Mg++ > Ca++ > Li+ > Na+ > K+. These nanocages may be potential sensors for these alkali and alkaline earth ions. [ABSTRACT FROM AUTHOR]

• The adsorption of CBrClF 2 on to the BNNT, BNAlNT, BNGaNT, BNPNT, and BNAsNT are studied. • To investigare the adsorption processes, the results of an NBO and QTAIM analyses are analyzed. • To find out the nature of intermolecular interactions aRDG diagrams are depicted. Nanostructures such as nanotubes and nanosheets are widely used in the medical industry for drug delivery, prevention, and treatment. These nanostructures are used as sensors or carriers by adsorbing functional groups. In this study, the adsorption rates of the bromochlorodifluoromethane (CBrClF 2) molecule, which is used as an effective gaseous fire suppression agent, onto the outer surfaces of pristine, Al, Ga, P, and As-doped boron nitride nanotubes are investigated. A periodic boundary condition density functional theory method using both Perdew, Burke, and Ernzerhof exchange–correlation (PBEPBE) and B3LYP-D3 functionals together with the 6-311G (d) basis set were used. Subsequently, the B3LYP, CAM-B3LYP, ωB97XD, and M06-2X functionals with the 6-311G (d) basis set were used to consider the single-point energies. Natural bond orbital analysis and the quantum theory of atoms in molecule were considered using the PBEPBE/6-311G (d) method, and the results were compatible with the expected electronic properties, namely the Wiberg bond index, natural charge, natural electron configuration, donor–acceptor natural bond orbital interactions, and second-order perturbation energies. All the calculations and analyses denoted that the adsorption of the CBrClF 2 molecule onto the surfaces of pristine boron nitride nanotubes occurred due to physical adsorption and van der Waals interactions. Among the doped nanotubes, the Al nanotube exhibited the highest adsorption energy compared to the other doped nanotubes. [ABSTRACT FROM AUTHOR]

The adsorption of CH 3 F, CH 3 Cl and CH 3 Br halomethanes on pristine boron nitride (BNNS), aluminum-doped boron nitride (BN(Al)NS) and Gallium-doped boron nitride (BN(Ga)NS) nanosheets were investigated by two-dimensional periodic boundary condition density functional theory methods. All nanosheets were geometrically optimized at B3LYP/6-311 + G (d) level, and single point energy calculation at M06-2X, ω B97X-D3 and CAM-B3LYP/6-311 + G(d) levels of theory were also performed. NBO and QTAIM analyses were also performed, and values of the Wiberg bond index (WBI), partial natural charges and donor-acceptor interactions were further analyzed. The obtained adsorption energy values (E ads) indicate that the tendency of nanosheets to adsorb CH 3 F and CH 3 Br to their surfaces are in the order of BN(Ga)NS > BN(Al)NS > BNNS. However, for CH 3 Cl, which adsorb with a significant lower E ads compared to the other halomethanes, this trend is as follows: BN(Al)NS > BN(Ga)NS > BNNS. Moreover, it was found that, the affinity of halomethanes to adsorb onto the surface of nanosheets is in the order of CH 3 Br > CH 3 F ≫ CH 3 Cl. Generally, it seems that BN(Al)NS and BN(Ga)NS are promising candidates in designing a new type of solid state halomethane gas sensors. Image 1 • The adsorption of CH 3 F, CH 3 Cl, and CH 3 Br onto the BN, Al/Ga-doped nanosheets. • Long-range corrected DFT study is also carried out. • NBO and QTAIM analyses are also performed. • The doping remarkably improves the sensor property of the BNNS. [ABSTRACT FROM AUTHOR]