The adsorption of toxic carbon dichalcogenides (CX2; X = O, S, or Se) on β12 borophene (β12) and ... more The adsorption of toxic carbon dichalcogenides (CX2; X = O, S, or Se) on β12 borophene (β12) and pristine graphene (GN) sheets was comparatively investigated. Vertical and parallel configurations of CX2⋯β12/GN complexes were studied herein via density functional theory (DFT) calculations. Energetic quantities confirmed that the adsorption process in the case of the parallel configuration was more desirable than that in the vertical analog and showed values up to −10.96 kcal/mol. The strength of the CX2⋯β12/GN complexes decreased in the order CSe2 > CS2 > CO2, indicating that β12 and GN sheets showed significant selectivity for the CSe2 molecule with superb potentiality for β12 sheets. Bader charge transfer analysis revealed that the CO2⋯β12/GN complexes in the parallel configuration had the maximum negative charge transfer values, up to −0.0304 e, outlining the electron-donating character of CO2. The CS2 and CSe2 molecules frequently exhibited dual behavior as electron donors ...
The efficacy of pure and aluminum (Al)-doped boron nitride nanocarriers (B12N12 and AlB11N12) in ... more The efficacy of pure and aluminum (Al)-doped boron nitride nanocarriers (B12N12 and AlB11N12) in adsorbing Chlormethine (CM), an anti-cancer drug, was comparatively dissected by means of the density functional theory method. The CM∙∙∙B12N12 and ∙∙∙AlB11N12 complexes were studied within two configurations, A and B, in which the adsorption process occurred via N∙∙∙ and Cl∙∙∙B/Al interactions, respectively. The electrostatic potential affirmations confirmed the opulent ability of the studied nanocarriers to engage in delivering CM via two prominent electrophilic sites (B and Al). Furthermore, the adsorption process within the CM∙∙∙AlB11N12 complexes was noticed to be more favorable compared to that within the CM∙∙∙B12N12 analog and showed interaction and adsorption energy values up to –59.68 and −52.40 kcal/mol, respectively, for configuration A. Symmetry-adapted perturbation theory results indicated that electrostatic forces were dominant in the adsorption process. Notably, the adsorp...
For the first time, σ-hole interactions within like⋯like carbon-containing complexes were investi... more For the first time, σ-hole interactions within like⋯like carbon-containing complexes were investigated, in both the absence and presence of the external electric field (EEF). The effects of the directionality and strength of the utilized EEF were thoroughly unveiled in the (F-C-F3)2, (F-C-H3)2, and (H-C-F3)2 complexes. In the absence of the EEF, favorable interaction energies, with negative values, are denoted for the (F-C-F3)2 and (H-C-F3)2 complexes, whereas the (F-C-H3)2 complex exhibits unfavorable interactions. Remarkably, the strength of the applied EEF exhibits a prominent role in turning the repulsive forces within the latter complex into attractive ones. The symmetrical nature of the considered like⋯like carbon-containing complexes eradicated the effect of directionality of the EEF. The quantum theory of atoms in molecules (QTAIM), and the noncovalent interaction (NCI) index, ensured the occurrence of the attractive forces, and also outlined the substantial contributions of...
The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets... more The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X3/X atom(s) of the NC-C6H2-X3 and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F3 and F-C-X3 (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (Eint) were observed for the F-C-F3∙∙∙NC-C6H2-X3 complexes compared with the F-C-F3∙∙∙NCX analogs. Moreover, significant Eint was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X3/X atom(s). Among Set I complexes, the highest negative Eint was ascribed to the F-C-F3∙∙∙NC-C6H2-I3 complex with a value of −1.23 kcal/mol. For Set II complexes, Eint values of F-C-X3 bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mo...
The versatility of striped borophene (sB), β12 borophene (β12), and pristine graphene (GN) to ads... more The versatility of striped borophene (sB), β12 borophene (β12), and pristine graphene (GN) to adsorb π-systems was comparatively assessed using benzene (BNZ) and hexafluorobenzene (HFB) as electron-rich and electron-deficient aromatic π-systems, respectively. Using the density functional theory (DFT) method, the adsorption process of the π-systems on the investigated 2D sheets in the parallel configuration was observed to have proceeded more favorably than those in the vertical configuration. According to the observations of the Bader charge transfer analysis, the π-system∙∙∙sB complexes were generally recorded with the largest contributions of charge transfer, followed by the π-system∙∙∙β12 and ∙∙∙GN complexes. The band structures of the pure sheets signaled the metallic and semiconductor characters of the sB/β12 and GN surfaces, respectively. In the parallel configuration, the adsorption of both BNZ and HFB showed more valence and conduction bands compared to the adsorption in the...
In the current study, unexplored type IV halogen⋯halogen interaction was thoroughly elucidated, f... more In the current study, unexplored type IV halogen⋯halogen interaction was thoroughly elucidated, for the first time, and compared to the well-established types I–III interactions by means of the second-order Møller–Plesset (MP2) method. For this aim, the halobenzene⋯halobenzene homodimers (where halogen = Cl, Br, and I) were designed into four different types, parodying the considered interactions. From the energetic perspective, the preference of scouted homodimers was ascribed to type II interactions (i.e., highest binding energy), whereas the lowest binding energies were discerned in type III interactions. Generally, binding energies of the studied interactions were observed to decline with the decrease in the σ-hole size in the order, C6H5I⋯IC6H5 > C6H5Br⋯BrC6H5 > C6H5Cl⋯ClC6H5 homodimers and the reverse was noticed in the case of type IV interactions. Such peculiar observations were relevant to the ample contributions of negative-belt⋯negative-belt interactions within the ...
Herein, the potentiality of carbon-containing molecules (W–C–F3, where W is a withdrawing atom or... more Herein, the potentiality of carbon-containing molecules (W–C–F3, where W is a withdrawing atom or group) to interact with Lewis bases (B), Lewis acids (A) and σ–hole-containing molecules (X2) with W–C···B/A/X2 angle of 180° was reported. −σ–hole and +σ–hole terminologies were implemented to describe the interactions of W–C–F3 with nucleophilic and electrophilic sites, respectively. To characterize such interactions, quantum mechanical calculations including geometrical optimization, ±σ–hole test, interaction energy calculation, quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index calculation were performed at MP2/aug-cc-pVTZ(PP) level of theory. The results showed (1) the electrostatic potentiality of the W–C–F3 molecules to favorably interact with Lewis bases and acids, (2) the dependency of ±σ–hole interaction energies on the σ–hole size of the tetrel atom and (3) descending of interaction energies in the order W–C–F3···B > W–C–F3···X2 > W–C–F3···A. QTAIM, and NCI calculations revealed the noncovalent nature of the ±σ–hole interactions. Further, an investigation on F–C–X3 model was carried out to highlight the emerging role of X3 atoms in ±σ–hole interactions. Comprising of the findings, the most favorable interaction energies were denoted when the F–C–X3 interact with X2 molecules compared to those with B and A molecules.
Three seminal types of noncovalent interaction, namely: hydrogen, halogen and tetrel interactions... more Three seminal types of noncovalent interaction, namely: hydrogen, halogen and tetrel interactions with π-systems, were investigated using quantum mechanical calculations.
The point-of-charge (PoC) approach was employed to investigate the characteristics of the tetrel ... more The point-of-charge (PoC) approach was employed to investigate the characteristics of the tetrel bond from an electrostatic perspective. W-T-XYZ···B nomenclature was suggested where T is a tetrel atom, W is the atom along the σ-hole extension, B is a Lewis base, and X, Y, and Z are three atoms on the same side of the σ-hole. Quantum-mechanical calculations were carried out on F-T-F systems (where T = C, Si, Ge, or Sn) at the MP2/aug-cc-pVTZ level of theory, with PP functions for Ge and Sn atoms. The tetrel bond strength was estimated via the molecular stabilization energy. Tetrel bond strength was found to increase with increasing PoC negativity (i.e., Lewis basicity) and the electronegativity of the W atom. Moreover, the effects of the T···PoC distance, the W-T···PoC angle, and the aqueous medium on the tetrel bond strength were also investigated. Correlations between tetrel bond strength and several atomic and molecular descriptors such as the natural charge on the tetrel atom, E,...
The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to parti... more The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to participate in tetrel- and halogen-bonding interactions was settled out, at the MP2/aug-cc-pVTZ level of theory, within a series of configurations for (X-T-X3)2 homodimers. The electrostatic potential computations ensured the remarkable ability of the investigated X-T-X3 monomers to participate in σ-hole halogen and tetrel interactions. The energetic findings significantly unveil the favorability of the tetrel···tetrel directional configuration with considerable negative binding energies over tetrel···halogen, type III halogen···halogen, and type II halogen···halogen analogs. Quantum theory of atoms in molecules and noncovalent interaction analyses were accomplished to disclose the nature of the tetrel- and halogen-bonding interactions within designed configurations, giving good correlations between the total electron densities and binding energies. Further insight into the binding energy phy...
Herein, a thorough comparative investigation for the potentiality of triel, tetrel, pnicogen, and... more Herein, a thorough comparative investigation for the potentiality of triel, tetrel, pnicogen, and chalcogen to engage in π-hole interactions with π-systems and Lewis bases was conducted. π-hole donors, namely, AlF3, SiF2O, PFO2, and SO3, were subjected to interact with benzene (BZN)/hexafluorobenzene (HFB) as electron-rich/electron-deficient π-systems and NH3, NCH, FH, and CO2 as Lewis bases. Using a wide range of quantum mechanical calculations, it was manifested that the investigated π-hole···π-system/Lewis base interactions exhibited preferential negative interaction energies with values up to −30.38 kcal/mol for AlF3···NH3 complex. π-hole···Lewis base complexes participated in a stronger π-hole bond than the π-hole···π-system analogs. In comparison, the reversed pattern was noticed for the π-hole···electron-deficient π-system. Quantum theory of atoms in molecules (QTAIM) analysis announced the closed-shell nature of all complexes under study except π-hole···NH3 interactions that...
σ-hole and lone-pair (lp) hole interactions of trivalent pnicogen-bearing compounds were comparat... more σ-hole and lone-pair (lp) hole interactions of trivalent pnicogen-bearing compounds were comparatively investigated under field-free and external electric field (EEF) conditions.
Chalcogen∙∙∙Chalcogen interactions were investigated within four types of like∙∙∙like and unlike ... more Chalcogen∙∙∙Chalcogen interactions were investigated within four types of like∙∙∙like and unlike Y=C=Y∙∙∙Y=C=Y complexes (where Y = O, S, and Se). A plethora of quantum mechanical calculations, including molecular electrostatic potential...
The adsorption of toxic carbon dichalcogenides (CX2; X = O, S, or Se) on β12 borophene (β12) and ... more The adsorption of toxic carbon dichalcogenides (CX2; X = O, S, or Se) on β12 borophene (β12) and pristine graphene (GN) sheets was comparatively investigated. Vertical and parallel configurations of CX2⋯β12/GN complexes were studied herein via density functional theory (DFT) calculations. Energetic quantities confirmed that the adsorption process in the case of the parallel configuration was more desirable than that in the vertical analog and showed values up to −10.96 kcal/mol. The strength of the CX2⋯β12/GN complexes decreased in the order CSe2 > CS2 > CO2, indicating that β12 and GN sheets showed significant selectivity for the CSe2 molecule with superb potentiality for β12 sheets. Bader charge transfer analysis revealed that the CO2⋯β12/GN complexes in the parallel configuration had the maximum negative charge transfer values, up to −0.0304 e, outlining the electron-donating character of CO2. The CS2 and CSe2 molecules frequently exhibited dual behavior as electron donors ...
The efficacy of pure and aluminum (Al)-doped boron nitride nanocarriers (B12N12 and AlB11N12) in ... more The efficacy of pure and aluminum (Al)-doped boron nitride nanocarriers (B12N12 and AlB11N12) in adsorbing Chlormethine (CM), an anti-cancer drug, was comparatively dissected by means of the density functional theory method. The CM∙∙∙B12N12 and ∙∙∙AlB11N12 complexes were studied within two configurations, A and B, in which the adsorption process occurred via N∙∙∙ and Cl∙∙∙B/Al interactions, respectively. The electrostatic potential affirmations confirmed the opulent ability of the studied nanocarriers to engage in delivering CM via two prominent electrophilic sites (B and Al). Furthermore, the adsorption process within the CM∙∙∙AlB11N12 complexes was noticed to be more favorable compared to that within the CM∙∙∙B12N12 analog and showed interaction and adsorption energy values up to –59.68 and −52.40 kcal/mol, respectively, for configuration A. Symmetry-adapted perturbation theory results indicated that electrostatic forces were dominant in the adsorption process. Notably, the adsorp...
For the first time, σ-hole interactions within like⋯like carbon-containing complexes were investi... more For the first time, σ-hole interactions within like⋯like carbon-containing complexes were investigated, in both the absence and presence of the external electric field (EEF). The effects of the directionality and strength of the utilized EEF were thoroughly unveiled in the (F-C-F3)2, (F-C-H3)2, and (H-C-F3)2 complexes. In the absence of the EEF, favorable interaction energies, with negative values, are denoted for the (F-C-F3)2 and (H-C-F3)2 complexes, whereas the (F-C-H3)2 complex exhibits unfavorable interactions. Remarkably, the strength of the applied EEF exhibits a prominent role in turning the repulsive forces within the latter complex into attractive ones. The symmetrical nature of the considered like⋯like carbon-containing complexes eradicated the effect of directionality of the EEF. The quantum theory of atoms in molecules (QTAIM), and the noncovalent interaction (NCI) index, ensured the occurrence of the attractive forces, and also outlined the substantial contributions of...
The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets... more The effects of Lewis basicity and acidity on σ-hole interactions were investigated using two sets of carbon-containing complexes. In Set I, the effect of Lewis basicity was studied by substituting the X3/X atom(s) of the NC-C6H2-X3 and NCX Lewis bases (LB) with F, Cl, Br, or I. In Set II, the W-C-F3 and F-C-X3 (where X and W = F, Cl, Br, and I) molecules were utilized as Lewis acid (LA) centers. Concerning the Lewis basicity effect, higher negative interaction energies (Eint) were observed for the F-C-F3∙∙∙NC-C6H2-X3 complexes compared with the F-C-F3∙∙∙NCX analogs. Moreover, significant Eint was recorded for Set I complexes, along with decreasing the electron-withdrawing power of the X3/X atom(s). Among Set I complexes, the highest negative Eint was ascribed to the F-C-F3∙∙∙NC-C6H2-I3 complex with a value of −1.23 kcal/mol. For Set II complexes, Eint values of F-C-X3 bearing complexes were noted within the −1.05 to −2.08 kcal/mol scope, while they ranged from −0.82 to −1.20 kcal/mo...
The versatility of striped borophene (sB), β12 borophene (β12), and pristine graphene (GN) to ads... more The versatility of striped borophene (sB), β12 borophene (β12), and pristine graphene (GN) to adsorb π-systems was comparatively assessed using benzene (BNZ) and hexafluorobenzene (HFB) as electron-rich and electron-deficient aromatic π-systems, respectively. Using the density functional theory (DFT) method, the adsorption process of the π-systems on the investigated 2D sheets in the parallel configuration was observed to have proceeded more favorably than those in the vertical configuration. According to the observations of the Bader charge transfer analysis, the π-system∙∙∙sB complexes were generally recorded with the largest contributions of charge transfer, followed by the π-system∙∙∙β12 and ∙∙∙GN complexes. The band structures of the pure sheets signaled the metallic and semiconductor characters of the sB/β12 and GN surfaces, respectively. In the parallel configuration, the adsorption of both BNZ and HFB showed more valence and conduction bands compared to the adsorption in the...
In the current study, unexplored type IV halogen⋯halogen interaction was thoroughly elucidated, f... more In the current study, unexplored type IV halogen⋯halogen interaction was thoroughly elucidated, for the first time, and compared to the well-established types I–III interactions by means of the second-order Møller–Plesset (MP2) method. For this aim, the halobenzene⋯halobenzene homodimers (where halogen = Cl, Br, and I) were designed into four different types, parodying the considered interactions. From the energetic perspective, the preference of scouted homodimers was ascribed to type II interactions (i.e., highest binding energy), whereas the lowest binding energies were discerned in type III interactions. Generally, binding energies of the studied interactions were observed to decline with the decrease in the σ-hole size in the order, C6H5I⋯IC6H5 > C6H5Br⋯BrC6H5 > C6H5Cl⋯ClC6H5 homodimers and the reverse was noticed in the case of type IV interactions. Such peculiar observations were relevant to the ample contributions of negative-belt⋯negative-belt interactions within the ...
Herein, the potentiality of carbon-containing molecules (W–C–F3, where W is a withdrawing atom or... more Herein, the potentiality of carbon-containing molecules (W–C–F3, where W is a withdrawing atom or group) to interact with Lewis bases (B), Lewis acids (A) and σ–hole-containing molecules (X2) with W–C···B/A/X2 angle of 180° was reported. −σ–hole and +σ–hole terminologies were implemented to describe the interactions of W–C–F3 with nucleophilic and electrophilic sites, respectively. To characterize such interactions, quantum mechanical calculations including geometrical optimization, ±σ–hole test, interaction energy calculation, quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index calculation were performed at MP2/aug-cc-pVTZ(PP) level of theory. The results showed (1) the electrostatic potentiality of the W–C–F3 molecules to favorably interact with Lewis bases and acids, (2) the dependency of ±σ–hole interaction energies on the σ–hole size of the tetrel atom and (3) descending of interaction energies in the order W–C–F3···B > W–C–F3···X2 > W–C–F3···A. QTAIM, and NCI calculations revealed the noncovalent nature of the ±σ–hole interactions. Further, an investigation on F–C–X3 model was carried out to highlight the emerging role of X3 atoms in ±σ–hole interactions. Comprising of the findings, the most favorable interaction energies were denoted when the F–C–X3 interact with X2 molecules compared to those with B and A molecules.
Three seminal types of noncovalent interaction, namely: hydrogen, halogen and tetrel interactions... more Three seminal types of noncovalent interaction, namely: hydrogen, halogen and tetrel interactions with π-systems, were investigated using quantum mechanical calculations.
The point-of-charge (PoC) approach was employed to investigate the characteristics of the tetrel ... more The point-of-charge (PoC) approach was employed to investigate the characteristics of the tetrel bond from an electrostatic perspective. W-T-XYZ···B nomenclature was suggested where T is a tetrel atom, W is the atom along the σ-hole extension, B is a Lewis base, and X, Y, and Z are three atoms on the same side of the σ-hole. Quantum-mechanical calculations were carried out on F-T-F systems (where T = C, Si, Ge, or Sn) at the MP2/aug-cc-pVTZ level of theory, with PP functions for Ge and Sn atoms. The tetrel bond strength was estimated via the molecular stabilization energy. Tetrel bond strength was found to increase with increasing PoC negativity (i.e., Lewis basicity) and the electronegativity of the W atom. Moreover, the effects of the T···PoC distance, the W-T···PoC angle, and the aqueous medium on the tetrel bond strength were also investigated. Correlations between tetrel bond strength and several atomic and molecular descriptors such as the natural charge on the tetrel atom, E,...
The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to parti... more The versatility of the X-T-X3 compounds (where T = C, Si, and Ge, and X = F, Cl, and Br) to participate in tetrel- and halogen-bonding interactions was settled out, at the MP2/aug-cc-pVTZ level of theory, within a series of configurations for (X-T-X3)2 homodimers. The electrostatic potential computations ensured the remarkable ability of the investigated X-T-X3 monomers to participate in σ-hole halogen and tetrel interactions. The energetic findings significantly unveil the favorability of the tetrel···tetrel directional configuration with considerable negative binding energies over tetrel···halogen, type III halogen···halogen, and type II halogen···halogen analogs. Quantum theory of atoms in molecules and noncovalent interaction analyses were accomplished to disclose the nature of the tetrel- and halogen-bonding interactions within designed configurations, giving good correlations between the total electron densities and binding energies. Further insight into the binding energy phy...
Herein, a thorough comparative investigation for the potentiality of triel, tetrel, pnicogen, and... more Herein, a thorough comparative investigation for the potentiality of triel, tetrel, pnicogen, and chalcogen to engage in π-hole interactions with π-systems and Lewis bases was conducted. π-hole donors, namely, AlF3, SiF2O, PFO2, and SO3, were subjected to interact with benzene (BZN)/hexafluorobenzene (HFB) as electron-rich/electron-deficient π-systems and NH3, NCH, FH, and CO2 as Lewis bases. Using a wide range of quantum mechanical calculations, it was manifested that the investigated π-hole···π-system/Lewis base interactions exhibited preferential negative interaction energies with values up to −30.38 kcal/mol for AlF3···NH3 complex. π-hole···Lewis base complexes participated in a stronger π-hole bond than the π-hole···π-system analogs. In comparison, the reversed pattern was noticed for the π-hole···electron-deficient π-system. Quantum theory of atoms in molecules (QTAIM) analysis announced the closed-shell nature of all complexes under study except π-hole···NH3 interactions that...
σ-hole and lone-pair (lp) hole interactions of trivalent pnicogen-bearing compounds were comparat... more σ-hole and lone-pair (lp) hole interactions of trivalent pnicogen-bearing compounds were comparatively investigated under field-free and external electric field (EEF) conditions.
Chalcogen∙∙∙Chalcogen interactions were investigated within four types of like∙∙∙like and unlike ... more Chalcogen∙∙∙Chalcogen interactions were investigated within four types of like∙∙∙like and unlike Y=C=Y∙∙∙Y=C=Y complexes (where Y = O, S, and Se). A plethora of quantum mechanical calculations, including molecular electrostatic potential...
Uploads
Papers by Nayra Moussa