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This study investigates the potential use of phosphomolybdic acid (POM) as an adsorbate for hazardous organic gases (CH3X, where X = F, Cl, and Br). Density functional theory (DFT) is employed to analyze the interaction between POM and the gases. Structural optimization using the TPSSh/Lanl2Dz level of theory is performed to determine the stable configurations. The adsorption energy of CH3X on POM is calculated to understand the adsorption capabilities and identify the most favorable complex. The results show that CH3F/POM has two optimal adsorption sites, while CH3Br/POM has a larger bond distance and stronger adsorption energy. CH3Cl/POM exhibits three bonding sites. The HOMO-LUMO energy difference decreases after binding, indicating improved conductivity. QTAIM, bond order, and NCI analysis reveal the inter- and intramolecular interactions and bond characteristics. Overall, POM is found to be suitable for adsorbing these gases, especially CH3Br. [ABSTRACT FROM AUTHOR]

This study explores intermolecular interactions between the polyoxometalate (POM) compound, decatungstate acid, and CX2O (X=H, F, Cl, and Br). Initial optimizations were conducted using the PBE0 and M06‐2X /Lanl2DZ level of theory, renowned for adsorption studies. Computational results revealed a notable sequential increase in binding affinity for reactive compounds on POM surfaces optimized with PBE0, TPSSH, M06‐2X, CAM‐B3LYP, and ωB97XD/Lanl2Dz methods. Interestingly, the findings indicated a high binding affinity between reactive compounds and POM surfaces, affirming M06‐2X functional suitability for studying decatungstate acid interactions. Additionally, adsorption energy (Eads) values were negative, indicating stable adsorption processes. Careful examination of quantum theory of atoms in molecules (QTAIM), natural charge calculations, and hybridization calculations unveiled impressive intermolecular interactions, with non‐covalent interactions (NCIs) revealing deep blue iso‐surfaces in (CH2O@POM) and (CF2O@POM) complexes, indicating significant electrostatic force of interaction and presence of hydrogen bond interactions, enhancing POM surface's gas interaction capacity and smooth sensing. The analyzed complexes displayed slight increases in HOMO‐LUMO energy gap compared to POM, with the order of increase as follows: CH2O@POM (0.0819 eV)>CF2O@POM (0.0772 eV)>CBr2O@POM (0.0747 eV)>CCl2O@POM (0.0705 eV), suggesting POM′s suitability as an adsorbent. The study's major findings reveal the effective adsorption of CBr2O and CH2O facilitated by hydrogen bond interactions on the POM surface, making decatungstate acid a potential adsorbent for removing polluting gases from the atmosphere. [ABSTRACT FROM AUTHOR]

The ability of carbon- and silicon-based nanotubes, including pure carbon, silicon carbide, and Ge-doped silicon carbide nanotubes (CNT, SiCNT, SiCGeNT, respectively), for sensing highly toxic dichlorosilane (H2SiCl2) are investigated using quantum chemistry calculations. The intermolecular interactions between the sensing material and the gas molecule have been investigated with the density functional theory calculations with a functional that includes dispersion terms. The selected method employed is B3LYP-D3 (GD3BJ)/6-311G(d), while other functionals including PBE0, ωB97XD, and M06-2X have been used for comparison. The quantum theory of atoms in molecules (QTAIM) analysis is employed to check the type of intermolecular interactions. Natural bond orbital (NBO) calculations have been used to deduce the bond orders. The findings of this work indicate that the adsorption of the H2SiCl2 is a physisorption process, which is very desirable for its function as a sensing element. The Ge-doped nanotube offers maximum adsorption energy in comparison to CNT and SiCNT. [ABSTRACT FROM AUTHOR]

In this study, an exploration of molecular interactions between CH 4 , CO, CO 2 , H 2 O, N 2 , NH 3 , NO, NO 2 , O 2 , SO 2 gas molecules and B 12 N 12 (Zn) nanocage is conducted using advanced computational techniques, ωB97XD/Def2tzvp, unraveling fundamental behaviors. Employing global optimization methods and sophisticated tools like the bee colony algorithm in ABCluster software, the research offers insights into energy adsorption processes, confirming molecular stability through DFT calculations. The determination of electrophilicity index values through conceptual DFT analysis sheds light on relative reactivity levels and charge transfer phenomena, emphasizing that in some cases the nanocage's role as a potential electron acceptor. Natural bond analysis of charge transfer direction and valence shell orbital interactions enriches understanding, supported by comprehensive parameter compilation and critical point visualization. Further confirmation of interaction types and strengths through G(r)/V(r) ratios and ELF values enhances comprehension through quantum theory of atoms in molecule analysis. Ultimately, this study contributes significantly to computational chemistry, laying foundations for molecular design and engineering advancements. It sets the stage for future progress in materials science and catalysis, promising innovation in sustainable energy solutions and technological development. [Display omitted] • Molecular interactions explored: CH 4 , CO, CO 2 , H 2 O, N 2 with B 12 N 12 (Zn) nanocage. • Advanced computational techniques employed: ωB97XD/Def2tzvp. • Insights into energy adsorption processes revealed. • Role as electron acceptor highlighted; charge transfer phenomena analyzed. • Contribution to computational chemistry for molecular design advancements. [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]

[Display omitted] • Fullerene-like nanocages (C 59 Al and C 59 Ga) exhibit exceptional gas adsorption properties. • State-of-the-art DFT method validates strong interaction between nanocages and DCS gas. • The frequency calculations have been performed to show the stability of structures. • QTAIM and NCI techniques provide unprecedented insights into non-covalent interactions. • Research paves the way for advanced gas detection technologies in various domains. Within the framework of this investigation, an array of fullerene-like nanocages, denoted as C 59 X (where X represents C, Si, Ge, B, Al, Ga, N, P, and As), has been deftly employed as adsorbent for the purpose of detecting H 2 SiCl 2 (DCS) gas. The detection mechanism utilized a state-of-the-art density functional theory (DFT) method, integrating four advanced functionals (PBE0, ωB97XD, M06-2X, and B3LYP-D3), in conjunction with 6-311G(d) basis set. The discerning outcomes derived from the rigorous NBO (Natural bond orbital) bond order analysis, specifically focusing on the intricacies of the Wiberg bond index (WBI), served as compelling validation, unequivocally affirming the remarkable interaction capabilities harbored by C 59 Al and C 59 Ga nanocages with the gas. Notably, the adsorption energy values recorded for C 59 Al and C 59 Ga fullerene-like nanocages were strikingly amplified, serving as further testimony to their exceptional potential as nanosorbents. It is essential to underscore the comprehensive investigations conducted, employing QTAIM (Quantum Theory of Atoms in Molecules) and NCI (Non-covalent Interactions) techniques, as they played an integral role in corroborating and further substantiating the preferential adsorption exhibited by C 59 Al and C 59 Ga nanocages in relation to DCS gas. The in-depth analyses facilitated by these advanced techniques have provided unprecedented insights into the complex interplay of intermolecular forces, notably robust van der Waals forces, underlying the non-covalent interactions involved in the adsorption process. In light of the multifaceted findings, it is unequivocally established that C 59 Al and C 59 Ga nanocages exhibit exceptional properties as nanosorbents, thereby rendering them supremely suited for the deployment as adsorbent in the precise and efficient detection of the elusive DCS gas. [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]

Abstract: In this work, the interactions of pristine, Al‐ and Ga‐doped single walled armchair (5,5) boron nitride nanotubes (BNNTs) with He, Ne, Ar and Kr rare gases (RGs) were fully investigated using several different density functional theory (DFT) functionals including pure‐GGA (PBEPBE), hybrid‐GGA (B3LYP), meta‐hybrid‐GGA (M062X) and long‐range‐corrected B3LYP (CAM−B3LYP) in combination with two 6–31G(d) and 6–311+G(d) basis sets. Natural bond orbital (NBO) and quantum theory of atoms in molecule (QTAIM) analyses were also performed to better understand the intermolecular interaction between RGs and nanotubes. The adsorption energies (Eads) indicate that RGs could be adsorbed on the surface of the BNNTs with the following trend: Ne > Kr > Ar > He. The Eads energies obtained using CAM−B3LYP method have also been found to be 13–18%, (for Ne−Kr) and 32–44% (for He−Ar) higher than those obtained from normal B3LYP functional. Moreover, analysis of the natural partial charges reveals the small charge transfer from RGs to BNNTs, which confirms the sensing of RGs by BNNTs. QTAIM analysis also supports the existence of close‐shell (non‐covalent) interactions between BNNTs and RGs. Generally, according to the obtained results, it can be concluded that, Al‐ and Ga‐doped BNNTs are remarkably more sensitive to RGs than pristine‐BNNT, and may be good candidates in designing new RG sensors. [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]

New and better materials with high energy density are of great concern to researchers. Therefore, the design and modeling of these materials is a growing area of research. In this study, DFT investigations have been carried out to enhance the cell voltage of metal-ion batteries (Li, Be, Na, Mg, K, and Ca-ion batteries) via endohedral encapsulation of halide ions inside gallium arsenide nanocages (Ga 12 As 12). During their application as anode electrodes in metal-ion batteries, the pure and halide encapsulated Ga 12 As 12 surfaces were studied. In order to investigate the effect of neutral and ionic interactions on the electrochemical and geometric properties, the binding energy (E ads) and quantum descriptors of the M/M+ ions in the Ga 12 As 12 nanocage have been studied. Cell voltages of 0.10, 5.94, 0.14, 3.43, 0.66, and 1.97 V for pure Ga 12 As 12 were obtained. Due to encapsulation, the change in the Gibbs free energy is ultimately increased and thereby, the cell voltage is enhanced for X-Ga 12 As 12 (X = F, Cl and Br) with the maximum increment from 5.94 V to 7.79, 7.57, and 7.55 V observed in Be/F@Ga 12 As 12 , Be/Cl@Ga 12 As 12 ,and Be/Br@Ga 12 As 12 , respectively. In addition, relatively greater cell voltages were obtained using Mg/F@Ga 12 As 12 , Mg/Cl@Ga 12 As 12 , and Mg/Br@Ga 12 As 12 with cell voltages of 6.78, 6.75, and 6.73 V respectively. F−ion encapsulation exhibits better performance than Cl− and Br− ions. The Gibbs free energy (ΔG) and cell voltage (V Cell) were also found to be significantly increased for alkali-earth metals when compared to alkali metals. This study provides conclusive scientific evidence that endohedral halide encapsulated Ga 12 As 12 nanocages are excellent for Li, Be, Na, Mg, K, and Ca-ion batteries, especially Be, Mg, and Ca-ion batteries. Hence, they can be employed in coupling future metal-ion batteries used in hybrid electric vehicles, portable electronics, computer electronics, etc. • DFT studies of GaAs nanoclusters for solar cell application. • Enhancing the cell voltage by encapsulation with halide ions. • Alkali metals exhibited stronger binding energies than alkali-earth metals. • Sterling ΔG and cell voltage (V Cell) were observed for the alkali-earth metals. • Endohedral encapsulation of Ga 12 As 12 with halide enhanced the V cell towards Li, Be, Na, Mg, K and Ca-ion batteries. [ABSTRACT FROM AUTHOR]

Vinyl chloride (VCM) or chloroethylene is reactive in the gaseous state and its adsorption with pristine armchair (5,5) carbon nanotube (CNT) and silicon carbide nanotube (SiCNT) has been studied. Germanium (Ge) element as an impurity has been introduced to silicon carbide structure (i.e. SiCGeNT) so as to increase the reactivity of the surface of SiCNT and thus increase the sensitivity of the adsorbent during the adsorption process. The B3LYP-D3(GD3BJ) hybrid functional has been used to optimize the isolated nanostructures and vinyl chloride as well as their clusters (gas/nanotube). In addition, energy single-point calculations were performed using ωB97XD, PBE0, B3LYP-D3(GD3BJ), and M06-2X functionals. The selected basis function is 6-311G(d), which is a good approximation to cover the integration space with respect to the constituent atoms of the molecules studied in this research. Wave function analysis including non-covalent interaction (NCI), natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM), have also been done to reveal the intermolecular interactions nature. The results of these analyses, which are calculated using B3LYP-D3(GD3BJ)/6-311G(d) level of theory, are in agreement with each other and emphasize that among the mentioned nanotubes, silicon carbide nanotube doped with Ge element is more sensitive with respect to gas adsorption. Therefore, it will be a good option to design and build a nanosensor. [Display omitted] • The interactions of VCM with CNT, SiCNT, and SiCGeNT 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 was performed to consider the non-covalent interactions. [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] • Geometry optimization of POM is investigated. • CO, CO 2 , H 2 S, NH 3 , NO, NO 2 , and SO 2 can trap by the POM compound. • NBO and QTAIM analyses are applied to understand intermolecular interactions. • Polyoxymethylene compounds are potential options to design gas sensor. The forthcoming research includes the efficacy of polyoxometalate (POM) compound as an adsorbent for the following pollutant gases CO, CO 2 , H 2 S, NH 3 , NO, NO 2 , and SO 2. The investigated complex was first optimized using TPSSh/LANL2DZ model chemistry to obtain the most stable geometry of the isolated and complex structures. After which the adsorption energy of the complex was ascertained in other to identify the complex with comparably stronger adsorption energy and the most stable complex. To understand the nature of intermolecular interactions occurring during the adsorption process, we carried out quantum theory of atoms in molecules (QTAIM) and natural bonding orbitals (NBO) calculations so as to carefully estimate the bond order of the studied complexes. It is very important to know the nature of conductivity of the complex being adsorbed as such this information is provided by the HOMO-LUMO energy gap. From energy gap considerations, there is increase as well as a corresponding decrease following the adsorption of each gas on polyoxometalate. The energy gap of the POM before adsorption was observed to be 0.602 eV, however upon adsorption of CO and CO 2 it was observed to increase to 0.608 eV and 0.618 eV, with a difference of 0.006 eV and 0.016 eV. The increase in band gap was accompanied with a sharp decrease as H 2 S gas was adsorbed on POM with band gap of 0.122 eV a reduction of 0.496 eV from the band gap of CO 2 @POM, which indicate an increase in adsorption rate with a less stability of the adsorption process. The overall consideration of the adsorption energy and band gap shows that POM adsorbed NO, NH 3 (NO@POM, NH 3 @POM) better since it had the highest adsorption energy; thus, NO and NH 3 would be more efficiently detected by polyoxometalate molecule. [ABSTRACT FROM AUTHOR]

[Display omitted] • The interaction of H 2 SiCl 2 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. The utilization of 2D materials and nanostructured composites as potential sensors and adsorbent surface for various molecular processes has increased tremendously with the upsurge in the use of sensors for various applications. In this work, the utilization of boron nitride nanosheet (BNNS) and its aluminium and gallium (BNAlNS and BNGaNS) doped derivatives as sensors for dichlorosilane (C 3 H 7 NO 3) have been studied computationally by employing the B3LYP-D3 model with the 6-311G(d) basis set as well as the PBE0, ωB97XD, and M06-2X functionals. The adsorption and sensing potential of these nanosheets was tested against the highly toxic and flammable dichlorosilane (C 3 H 7 NO 3) gas molecule. Adsorption interactions of the gas with the nanosheets was computed and reported. To understand the type of intermolecular interactions occurring during the adsorption process, quantum theory of atoms in molecules (QTAIM) and natural bond orbital analysis (NBO) for the estimation of bond order was computed and reported. The reactivity and sensing attributes of the studied nanosheets were further appraised by the conceptual density functional theory (CDFT) and HOMO-LUMO energy gap. The computed energy gap shows a decreasing trend upon adsorption of DCS gas, the obtained values for the nanostructures were as follows: BNNS: 5.729, BNAlNS: 5.739, and BNGaNS: 5.742 eV. The results of the adsorption interaction divulged that the gallium doped nanosheet (BNGaNS) exhibited higher adsorption properties and sensitivity towards DCS gas when compared with other studied derivatives. [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 boron nitride nanotube (BNNT), Al-doped boron nitride (BAlNNT), and BC2N nanotube nanotubes (BC2NNT) have been used to use their outer surface as a suitable substrate for the adsorption of the Fluorouracil (5-FU) drug molecule. The computational framework used in the study of intermolecular interactions of species participating in the adsorption process was density functional theory (DFT). Various functionals, including PBE0, M06-2X, ωB97XD, and B3LYP-D3 have been employed to study the effects of electronic properties well. Also, the successful basis set 6-311G(d) has been used in all calculations. Different wave function analyses have been used to determine the type of intermolecular interactions, including natural bond orbital (NBO), non-covalent interactions (NCI), quantum theory of atoms in molecules (QTAIM) using B3LYP-D3/6-311G(d) model chemistry. All methods reveal the consistency and physical adsorption of the drug molecule onto the nanostructures. The strength and sensitivity of adsorption between the mentioned nanotubes are BAlNNT > BC2NNT > BNNT. The HOMO–LUMO energy gaps are found to be 6.545, 8.127, and 7.027 eV for BNNT, BNAlNT, and BC2NNT respectively, and depicted through the density of states (DOS) diagrams. Higher 5-FU drug adsorption energy for Al-doped BNNT indicates that the Al-doped BNNT can be used to design a 5-FU drug nanocarrier. [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]

[Display omitted] • The interaction of CH 2 N 2 with X 12 O 12 (X = Be, Mg) nanocages 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. The feasibility of detecting diazomethane (CH 2 N 2) in the gas phase by adsorption onto the exterior surface of inorganic-based X 12 O 12 (where X can be Be, Mg, or Ca) nanocages is investigated here using DFT. All the structures, including those of the pristine CH 2 N 2 and of the nanocages, as well as of the CH 2 N 2 /nanocage systems, have been optimized using the B3LYP-D3, M06-2X, ωB97XD, and CAM-B3LYP functionals, in conjunction with 6-311G(d) basis set. NBO, NCI, and QTAIM analyses results are in good agreement with each other. Furthermore, the Density Of States (DOSs), the natural charges, the Wiberg Bond Indices (WBI), and natural electron configurations were considered to investigate the nature of intermolecular interactions. The energy calculations indicate a strong size-dependent adsorption, with the nanocages comprised of large atoms being able to attract CH 2 N 2 more strongly, and hence bind with it more effectively. The adsorption incurs also significant changes to HOMO and LUMO energies. [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]