DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages

Accepted Manuscript DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages Hamidreza Jouypazadeh, Hossein Farrokhpour PII:

S0022-2860(18)30340-5

DOI:

10.1016/j.molstruc.2018.03.051

Reference:

MOLSTR 24990

To appear in:

Journal of Molecular Structure

Received Date: 4 August 2017 Revised Date:

13 March 2018

Accepted Date: 13 March 2018

Please cite this article as: H. Jouypazadeh, H. Farrokhpour, DFT and TD-DFT study of the adsorption and detection of sulfur mustard chemical warfare agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages, Journal of Molecular Structure (2018), doi: 10.1016/ j.molstruc.2018.03.051. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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ACCEPTED MANUSCRIPT DFT and TD-DFT Study of the Adsorption and Detection of Sulfur Mustard Chemical Warfare Agent by the C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages

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Hamidreza Jouypazadeh* and Hossein Farrokhpour*

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Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran

Corresponding Authors: Hamidreza Jouypazadeh: E – mail: [email protected] Hossein Farrokhpour: E – mail: [email protected]

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Abstract In the present research, the interaction of sulfur mustard, a chemical warfare agent, with the surface of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages

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was studied using the dispersion corrected density function theory (DFT-D3) method. The calculated adsorption energies of sulfur mustard on the surface of the nanocages showed that the Al12N12, C12Si12 and Mg12O12 are useful for the adsorption of the sulfur mustard. The

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quantum theory atom in molecule (QTAIM) analysis was used to study the nature of interactions of sulfur mustard with the surface of the selected nanocages. Based on QTAIM

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analysis, the majority of interactions of sulfur and chlorine atoms of sulfur mustard with the surface of the considered nanocages are covalent and quasi covalent whereas the interactions of hydrogen atoms of sulfur mustard with the surface of the nanocages are generally noncovalent. The charge transfer between sulfur mustard and the nanocages as well as chemical

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quantum descriptors of complexes were calculated using natural bond orbital (NBO) method. The most electron charge transfers from the sulfur mustard to B12N12 nanocage where the S atom of sulfur mustard donor a chemical bond to B atom of the nanocage. The ability of the

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considered nanocages for detecting sulfur mustard was studied using time-dependent density

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function theory (TD-DFT) and density of state (DOS) diagram. It is found that the C24, Al12P12, Be12O12 and B12N12 nanocages are useful sensors for this chemical agent.

Keyword: Sulfur Mustard, Adsorption, Detection, Nanocage, DFT-D3, TD-DFT

ACCEPTED MANUSCRIPT Introduction Bis-(2-choloroethyl) sulfide, that often called sulfur mustard due to its odor, is a very persistent toxic material that introduced during World War I as a chemical warfare agent (CWA) [1]. Sulfur mustard has low solubility in water but, dissolves in fats simply, therefore

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can permeate in the body skin and poison its victim. This agent affects DNA with alkylating it and prevents from the proliferation of cells [2-4]. Sulfur mustard was used in many wars during the 20th and 21th centuries, such as Italy-Libya (1930), Egypt-North Yemen (1963-67),

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Iraq-Iran (1983-88) [1], ISIS-Kurdish (2015) [5, 6] wars and is responsible for the death of thousands of civilian and military people. Therefore, finding suitable compounds which can

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sense, adsorb or destroy this agent is urgent for scientists.

With regard to the more surface of nanostructures compared to the bulk materials, the nanostructures can be suitable for detecting, adsorbing and destroying of sulfur mustard and other CWAs. In recent years, scientists pay an especial attention to study of nanostructures in

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order to detect, adsorb, and detoxify the CWAs. Procell et al. investigated the reaction of sulfur mustard and nerve agents with AP-Al2O3 nanoparticles using 31P, 13C and 27Al MASS NMR [7]. SnO2, WO3, In2O3, CuO and Y2O3 nanopowders were also used for the sensing of

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sulfur mustard, sarin and soman by Tomchenko at el. [8]. In several separated studies,

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adsorption and detoxification of sulfur mustards on the reactive surface of MnO nanotubes and nanosheets were investigated [9-12]. Also, TiO2 [13, 14], VO2 [15], ZnO [16], and CeO [17, 18] nanostructures are other compounds, which have been studied for the adsorption and detoxification of sulfur mustard in recent years. To our knowledge, although a few theoretical studies were performed on the detection, adsorption and decomposition of CWAs on the surface of the nanostructures [19-22]. In the present work, the density function theory (DFT), Natural bond orbital (NBO) and Quantum theory of atoms in molecule (QTAIM) were

ACCEPTED MANUSCRIPT employed to investigate the potential of C24, C12Si12, Al12N12, Al12P12, B12N12, Be12O12 and Mg12O12 nanocages in order to detect and adsorb the sulfur mustard CWA.

Computational Details

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The structures of sulfur mustard and nanocages were taken from literature [23-32] and their geometries, as well as their complexes, were optimized using B3LYP-D3 level of theory [33, 34] accompanied with 6-31g(d) basis set. The frequency calculations were performed on

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the optimized structures to confirm they are in a local minimum of potential energy surface. Also, the zero-point energy correction was obtained from the frequency calculations. The

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adsorption energies (Eads) of sulfur mustard on the surface of the nanocages were obtained by Eq. 1.

Eads =Ecomplex − Enanocage − ESM (1) where Ecomplex shows the energy of sulfur mustard complex and Enanocage and ESM are isolated

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energies of nanocage and sulfur mustard monomers, respectively. The Eads was formed from interaction energy (Eint) between the sulfur mustard and nanocage with their geometries in the complex and the summation of deformation energies of monomers (Edef) during the

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adsorption process. (eq. 2-6).

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Eads =Eint +Edef (2) Eint =Ecomplex − Enanocage-in complex − ESM-in complex (3) Edef-nanocage =Enanocage-in complex − Enanocage (4) Edef-SM =ESM-in complex − ESM (5) Edef = Edef-nanocage + Edef-SM (6)

ACCEPTED MANUSCRIPT where Enanocage-in complex and ESM-in complex show the energies of nanocage and sulfur mustard with their geometries in the complex. To confirm the accuracy of Eads and Eint ,obtained at the B3LYP-D3/6-31g(d) level of theory, the single-point energy calculations were performed on the optimized geometries with the larger basis set (6-31++g(d,p)) and the same DFT

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functional and Eads and Eint were calculated. The counterpoise method was used to correct the Eads and Eint for basis set superposition error (BSSE) [35]. All calculations were performed using GAUSSIAN 09 quantum chemistry program [36].

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The NBO analysis was used to calculate the charge transfer between sulfur mustard and nanocage [37]. For better understanding the charge transfer, the difference map of

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electron density of adsorption of the sulfur mustard on the surface of the nanocages was calculated using Multiwfn 3.4 [38]. The quantum theory of atom in molecule (QTAIM) analysis was employed to investigate the nature of bond formation between sulfur mustard and nanocage during the adsorption process [39]. The energy gap (Eg) between the highest

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occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) was calculated to investigate the conductivity of the structures [40-42]. (eq. 7-12). Eg =(εL -εH )

(7)

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where εL and εH are HOMO and LUMO energies, respectively. Also, electronic density of

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state (DOS) diagrams (with FWHM=0.3 eV) were calculated using GaussSum program [43] for nanocages and sulfur mustard-nanocage complexes. The time-dependent density-functional theory (TDDFT) is an extension of the

ground-state density-functional theory (DFT) and is properly used for the study of electronic excitations in atoms and molecules. In fact, the TDDFT is an alternative formulation of timedependent quantum mechanics which uses the one-body electron density, n(r, t) instead of normal approach in quantum mechanics which uses the wave-functions and the many-body Schr¨odinger equation. The standard method for obtaining n(r, t) is with the help of a

ACCEPTED MANUSCRIPT fictitious system of noninteracting electrons, the Kohn-Sham system. In this case, the equations are simply solved using numerical methods even for the systems with a large number of atoms. These electrons feel an effective potential, the time-dependent Kohn-Sham potential[44-46]. In present work, the UV-visible spectra of sulfur mustard, nanocages and

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their related complexes were calculated by the TD-DFT at the B3LYP-D3/6-31g(d) level of theory. The fifty excited state were considered in the TD-DFT calculations. The half width at half maximum (HWHM) equal to 0.1 eV was used for the simulation of the UV spectra.

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NBO.5 program [47] was used for the assignment of the electronic transitions.

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Results and Discussions

Structures and Map of Electrostatic Potential of Sulfur Mustard and Nanocages Nadas et al. investigated the structures of different conformers of sulfur mustard using MP2/aug-cc-pVDZ level of the theory [26]. They found 23 unique conformers for sulfur

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mustard. The most stable conformer of sulfur mustard, which has been shown in Figure 1, belongs to C2 symmetry point group. Figure 1 also shows the map of electrostatic potential (MEP) of sulfur mustard. The minimum and maximum of potential (Vmin and Vmax),

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identified with the blue and red dots respectively, indicate the maximum values of an

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aggregate of negative and positive charges on the electrostatic surface of the molecule. As seen in Figure 1, the most aggregate of positive charge has been located in the vicinity of hydrogen atoms and the most aggregate of negative charge are around chlorine and sulfur atoms.

The structures of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages have been investigated in literature and the most stable structure of each nanocage have been determined[23-32]. These nanocages have six tetragonal and eight hexagonal rings except C24. The most stable C24 nanocage is constituted from twelve pentagonal and two

ACCEPTED MANUSCRIPT hexagonal rings. The structure of Al12N12 and C24 nanocages, as well as their MEPs, have been showed in Figure 2. The structures and MEPs of other nanocages are similar to Al12N12. The X12Y12 (X=Si, B, Al, Be and Mg, Y=C, N, P, and O) nanocages have two kinds of Vmax which located in X atoms and center of hexagonal rings and one kind Vmin which located in Y

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atoms. The Values of Vmax located in X atoms are very larger than those located in the center of hexagonal rings. Also, the C24 has two kinds of Vmax and Vmin with low absolute value. The most important values of Vmax and Vmin of sulfur mustard and each nanocage have been

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reported in Table 1. The difference between Vmin of sulfur mustard and Vmax nanocage (or Vmax of sulfur mustard and Vmin nanocage) can get an outline about the favorite orientations

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of sulfur mustard on the surfaces of nanocages. Based on Table 1, it is predicted that the favorite orientations are those which contain interaction of chlorine and sulfur atoms of sulfur mustard with X atoms of X12Y12 (X=B, Al, Be, Mg and Si, Y=N, P, O, and C).

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Optimized structures of complexes and QTAIM analyses

To find all of the different geometries of each complex formed from the adsorption of sulfur mustard on the surface of each nanocage, the molecule was placed on the surface of

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each nanocage from the different orientations and the optimization was performed. The

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calculated MEP of the molecule and nanocages used to distinguish the preferred initial orientations for the optimization. Totally, 6, 6, 4, 5, 6, 6 and 5 different geometries were obtained for the adsorption sulfur mustard on the surface of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages, respectively. The Eads, Eint and corrected zero-point adsorption energies (∆E0) of different geometries related to each sulfur mustard-nanocage complex were found in Table 2. As seen in Table 2, the strongest and weakest adsorbent of sulfur mustard among the selected nanocages are Al12N12 and C24, respectively. It has been generally accepted that the threshold adsorption energy to distinguish the chemisorption

ACCEPTED MANUSCRIPT processes from the physisorption processes is about 11kcal/mol (0.5 eV) [48]. Therefore, sulfur mustard can chemisorb on the surface of all selected nanocages except for C24. The values of Eads of sulfur mustard on C24 nanocage varies in the range of -1.649 to -5.973 kcal/mol which are lower than threshold chemisorption energy.

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Figure 3 shows the most stable geometry of complex related to each nanocage based on their calculated ∆E0s. The other optimized geometries of complexes have been demonstrated in Figure S1-S7 in electronic supporting information. As depicted in Figure 3,

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interaction of sulfur atom with X atom is the most interaction in C12Si12, Al12N12, Al12P12, Be12O12 and B12N12 nanocages. There are simultaneous interaction of two chlorine atoms of

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sulfur mustard with Mg and C atoms of Mg12O12 and C24 in the most stable geometries of complexes related to these nanocages. To investigate the nature of the adsorption of sulfur mustard on the surface of nanocages, the QTAIM analysis was performed and the results were reported in Table 3 for the most stable geometry of complexes shown in Figure 3 and

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Tables S1-S7 for other geometries. This analysis contains the electron density (ρ), the Laplacian of electron density (∇  ), the density of kinetic energy (G), the density of potential energy (V), the density of total energy (H) and the absolute ratio of V and G (|V/G|).

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|V/G|>2, ∇  and H <0 are characteristics of covalent band. Also, |V/G|<1, ∇  and H

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>0 are indicative of non-covalent band [49]. As shown in Table 3 and also Tables S1 to S7, the value of |V/G| of the interaction of hydrogen atoms of sulfur mustard with Y atom of nanocages in all complexes except Mg12O12 are lower than 1 and also their ∇  and H are positive which show that these interactions are non-covalent. The value of |V/G|, ∇  and H of interactions of Cl and S atoms of sulfur mustard with the C atoms of C24 are about those of interaction of hydrogen atoms with C atoms in this nanocage which shows that these interactions are non-covalent too. The majority of interactions of Cl and S atoms with X atoms in C12Si12, Al12N12, Al12P12, Be12O12 have 2>|V/G|>1, H<0 and ∇  >0 which shows

ACCEPTED MANUSCRIPT that these interactions are weak covalent bond. Interaction of S atom of sulfur mustard with B atom in two more stable geometries related to B12N12 nanocage have |V/G|>2, ∇  and H<0 which is indicative of covalent nature of this bond. The majority of interactions of S and Cl atoms with B atoms in other geometries of sulfur mustard-B12N12 complex are weak

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covalent bond. In Sulfur-Mustard-Mg12O12 complex, the interaction of hydrogen atoms of sulfur mustard with O atoms of nanocage are more important than interactions of S and Cl atoms of sulfur mustard with the Mg atoms of cage. The QTAIM analysis shows that the

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majority of the interactions of hydrogen atoms of sulfur mustard with the surface of nanocage can be classified as weak covalent or strong non-covalent bond whereas interactions of Cl

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and S atoms of sulfur mustard with the Mg atoms of the nanocage have non-covalent nature except for structure d.

NBO analysis

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The charge transfer (Q) of adsorption of sulfur mustard on the surface of nanocages have been reported in Table 4. As seen in Table 4, the calculated values of Q are negative for all geometries except for two less stable geometries related to C24 nanocage. The negative

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value of Q is indicative of electron charge transfer from sulfur mustard to nanocage. The

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most charge transfer occurs in two more stable geometries of the adsorption of sulfur mustard on the surface of B12N12. The reason for this can be the formation of covalent bond between the S atom of sulfur mustard with B atom of the surface of nanocage. To visualize the charge transfer between sulfur mustard and nanocages, the map of difference electron density between complexes and monomers in their complex geometries was calculated for the most stable geometry of each complex (see Figure 4). In Figure 4, the blue and red part are indicative of the decrease and increase of electron density, respectively.

ACCEPTED MANUSCRIPT Table 4 also tabulated the energy of the highest occupied molecular orbital (ƐHOMO), the energy of the lowest unoccupied molecular orbital (ƐLUMO) and the energy gap between HOMO and LUMO (Eg). The decrease of Eg is indicative of the increase of conductivity. As reported in Table 4, the Eg of nanocages do not considerably change after adsorption of

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sulfur mustard on them except for Be12O12 and B12N12. The Eg of Be12O12, which is 8.288 eV, decrease to 7.334 eV due to the adsorption of sulfur mustard on it in the most stable geometry. Therefore, the electroconductivity of this nanocage increases after the adsorption.

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Also, the adsorption of sulfur mustard on the surface of B12N12 decreases Eg from 6.839 eV to 6.427 eV in its most stable geometry. The change in the electroconductivity of nanocage

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due to adsorption of a chemical material can be used as a detectable property for sensing of that material. Therefore, Be12O12 and B12N12 can be a good sensor for sulfur mustard. The diagrams of the density of states (DOS) visualize the change of the value of Eg of nanocages due to the adsorption of sulfur mustard on them. The diagrams of DOS of nanocages and the

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most stable geometry relative to each nanocage have been shown in Figure 5. The diagrams of other geometries have been listed on Figure S8 to S14.

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The UV Absorption Spectra

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The sulfur mustard can be adsorbed on the surface of each nanocage in different orientations and make different geometries for each complex whereas each geometry has its own absorption spectrum. In large scale, the possibility of each orientation of the sulfur mustard on the surface of a nanocage is the same and only the adsorption energy determines the possibility of the formation of the complex in that orientation. The observable absorption spectrum of each complex is a superposition of absorption spectra of its different geometries so that portion of more stable geometries is more. In this work, the portion of each geometry in the absorption spectrum of each complex was determined using Boltzmann ratio:

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$(%& $%( )  = # )* (13) !

where k is the Boltzmann constant, T is the temperature, and E0 is the zero point corrected adsorption energy. Figure 6 compares the Boltzmann average absorption spectrum of each

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complex with its corresponding isolated nanocage. The details of the absorption spectra of different geometries and their portion in Boltzmann average spectrum of each complex have been displayed in Figures S15 to S21. Also, the assignment of these spectra and their orbital

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combinations have been tabulated in Tables S8-S21.

Figures 6A compares the UV spectrum of C24 nanocage and its Boltzmann average

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UV spectrum of its corresponding complex. As seen in this figure, the C24 nanocage has an intense peak as well as two peaks with lower intensity in the range of 240-380 nm and a medium peak in the visible area. The adsorption of sulfur mustard on the surface of this nanocage merges three peaks situated in 240-380 nm and partly decreases the intensity of the

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main peak, adds two peaks with low intensity in the visible area but, without appreciable effects on the peak situated in the visible area at the C24 spectrum. The investigation of the absorption spectra of each geometry shows that adsorption sulfur mustard on the surface of

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the nanocage in the d and f labeled geometries can considerably change the UV spectrum of the nanocage but their portion is low (about 8%) in the average spectrum because of their low

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zero-point corrected adsorption energies (see Figure S15). To precisely study, the main electronic transitions which form peaks of spectra of C24 and its relative complexes were investigated using canonical molecular orbital (CMO) analysis. The electronic transitions and their CMO analyses of C24 and its related complexes were tabulated in Table S8 and S15. As shown in Table S8, the main electronic configuration of the most intense transition in the C24 spectra is consisted of superposition of HOMO-1
LUMO+8 and HOMO
LUMO+9 excitation. Also, HOMO-2
LUMO+2 is the most transition that forms the most important line of the peak located in visible area. As seen in Table S15, HOMO and HOMO-1 orbitals

ACCEPTED MANUSCRIPT have been consisted of 2-center bond orbitals (BD) of C-C bonds shared between pentagonal and hexagonal rings (5-6 CCBs) whereas LUMO+8 and LUMO+9 orbitals have been consisted of 2-center non-bonding orbitals (BD*) of C-C bonds shared between two pentagonal rings (5-5 CCBs). Therefore, the electronic transition from BDs of 5-6 CCBs to

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BD*s of 5-5 CCBs is the reason for the presence of main peak of UV spectrum of C24 in the range of 240 to 380 nm. Also, BDs of 5-5 CCBs and BD*s of 5-6 CCBs dominate the HOMO-2 and LUMO+2 orbitals, respectively. Therefore, the peak placed on visible area in

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UV spectrum of C24 is due to electronic transition from BDs of 5-5 CCBs to BD*s of 5-6 CCBs. The a labeled geometry of the complex dominates the UV average spectrum of the

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sulfur mustard-C24 complex and is responsible for merging of peaks in 240-380 nm area. The main electronic configuration of the most intense line in 240-380 nm region has been composed from two electronic transitions from BDs of 5-5 CCBs and 5-6 CCBs to BD*s of 5-5 CCBs. The appearance of the line located at 322.79 nm is the reason for merging of peaks

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in 240-380 nm area. This line is mainly related to the electron transition from the lone pairs (LP) of Cl atoms of the sulfur mustard to BD*s of 5-5 CCBs. The peak situated on visible area of UV spectrum of C24 do not appreciably change after adsorption of sulfur mustard on

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its surface. Based on Figure S15, the f labeled geometry is responsible for adding of two new

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peaks in visible area (380-400 and 500-540 nm regions). The CMO analysis shows that these peaks are originated from electronic transitions from the LP of S atom of sulfur mustard to BD*s of 5-5 CCBs and 5-6 CCBs of C24, respectively. Because the intensity of these two peaks are comparable to peak situated in 550-650 area, adsorption of sulfur mustard on the C24 nanocage can change its color and therefore, the C24 nanocage can use as a good sensor for sulfur mustard. The average UV spectrum of the sulfur mustard-C12Si12 complex was compared with the spectrum of C12Si12 nanocage in Figure 6B. The UV spectrum of C12Si12 nanocage have

ACCEPTED MANUSCRIPT two main peaks: one intense peak in 300-340 nm area and the other one in visible area. Based on Table S9, electronic transition from BDs of X-Y bonds shared between hexagonal rings (6-6 XYB) to BD*s of 6-6 XYBs is the origin of the appearance of both peaks. The adsorption of sulfur mustard on the surface of C12Si12 decreases the intensity of the peak

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placed in 300-340 nm area and shifts the peak situated in visible area to shorter wave lengths that can change the color of the nanocage due to adsorption of sulfur mustard. Therefore, this nanocage can be a good sensor for sulfur mustard. The spectrum of a labeled geometry of

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complex dominates the average UV spectrum of complex. The main peak of spectrum of a labeled geometry located in 300-340 nm is formed from two lines with wave lengths of

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318.44 and 320.77 nm. Assignment of these lines shows that the line at 318.44 nm is due to the superposition of HOMO
LUMO+7 and HOMO-1
LUMO+7 transitions and the line at 320.77 nm is due to HOMO-2
LUMO+6 transition. The precise investigation of molecular orbitals participated in these transitions shows that HOMO and HOMO-1 are

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dominated with the BDs of 6-6 XYBs of horizontal cincture of nanocage whereas HOMO-2 is formed from the BDs of 6-6 XYBs of vertical cincture of nanocage. Also, LUMO+6 and LUMO+7 consist of the BD*s of 6-6 XYBs of vertical and horizontal cincture, respectively.

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Therefore, the electron transition from BDs of 6-6 XYBs of horizontal cincture to BD*s of 6-

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6 XYBs of horizontal cincture and BDs of 6-6 XYBs of vertical cincture to BD*s of 6-6 XYBs of vertical cincture are reasons for the appearance of the lines at 318.44 and 320.77 nm, respectively, whereas, the investigation of HOMO-1 and HOMO-2 of isolated nanocage shows that these MOs are composition of BDs of 6-6 XYBs of two cinctures. In addition, the LP of a C atom (C14), adjacent to the place of adsorption of sulfur mustard, is contributed to the formation of HOMO of the complex. The probable reason for the decrease of intensity of peak situated at 300-340 nm area could be attributed to the change of the contribution of natural orbitals of HOMO-1 and HOMO-2 from the composition of BDs of two cinctures in

ACCEPTED MANUSCRIPT isolated nanocage to BDs of one cincture and the contribution of LP of C atom in HOMO of complex. The most important line of the peak in visible region is located at 359.57 nm. This line based on Tables S9 and S16 is related to the electron transition from BD of 6-6 XYBs of horizontal cincture to BD* of one 6-6 XYB (Si10-C15) which is in the vicinity of the place of

C15 bond contributes to formation of line at 359.57 nm.

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adsorption of sulfur mustard. In addition, electron transition from LP of C14 to BD* of Si10-

Figure 6C shows the average UV spectrum of sulfur mustard-Al12N12 complex in

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comparison to the spectrum of Al12N12 nanocage. The spectrum of Al12N12 shows a peak in 240-280 nm area which has been composed from two overlapped peaks. As seen in Table

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S10, the electronic transition from BDs of bonds shared between tetragonal and hexagonal rings (4-6 XYB) to BD*s of 6-6 XYBs are responsible for the appearance of more intense peak and less intense peak is due to the electronic transition from BDs of 4-6 XYBs to BD*s of 4-6 XYBs. The adsorption of sulfur mustard on the surface of Al12N12 nanocage decreases

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intensity of this peak and adds a peak with low intensity in 280-310 nm. The average UV spectrum of complex is dominated by the spectrum of b labeled geometry. Based on Table S10, the superposition of the electronic transition from BDs of 6-6 XYBs of nanocage to

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BD*s of 4-6 XYBs of nanocage and bonds of the sulfur mustard are responsible for the

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formation of peak in 240-280 nm area in the spectrum of b labeled geometry. The second peak forms from two lines at 290.90 and 295.36 nm. The assignment of these lines shows that the superposition of the electronic transition from BDs of 4-6 XYBs and 6-6 XYBs of nanocage to BD*s of C-Cl bonds of sulfur mustard and the electronic transition from BDs of 6-6 XYBs in the vicinity of the position of the adsorption to a BD* of a 6-6 XYB in the other side of the nanocage are responsible for these lines, respectively. These changes in the average UV spectrum of the complex in comparison to spectrum of nanocage are not so appreciable, therefore, Al12N12 nanocage cannot be used as a sensor of the sulfur mustard.

ACCEPTED MANUSCRIPT Figure 6D compares the average UV spectrum of sulfur mustard-Al12P12 complex with the spectrum of Al12P12 nanocage. The UV spectrum of Al12P12 nanocage has three peaks: two peaks in 300-350 nm area and one peak with low intensity in visible area. The superposition of electronic transition from BDs of 4-6 XYBs and 6-6 XYBs to unfilled

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valance lone pairs (LP*) of Al atoms forms the peaks located at 300-350 nm area. The peak situated in the visible area is due to the electronic transition from LPs of P atoms to LP*s of Al atoms. As seen in Figure 6D, the intensity of three peaks of the spectrum of the nanocage

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have considerably increased because of the adsorption of sulfur mustard. Among these, the increase of intensity of peak placed in the visible area can help for color sensing of sulfur

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mustard by this nanocage. Therefore, the Al12P12 nanocage can be a useful sensor for the detection of sulfur mustard. The absorption spectra of different geometries of this complex are compared together and with the spectrum of the nanocage in figure S18. Also, the assignment of the spectra of the nanocage and related complexes tabulated in Tables S11 and

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S18. The a and d labeled geometries have the most contribution in the average UV spectrum of complex and the contribution of other geometries is negligible. Based on Table S11, the electronic transition from BDs of 4-6 XYBs to BD*s of 4-6 XYBs is reason for appearance of

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the intense peak at 300-350 nm area of spectra of both geometries. Also, the electronic

area.

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transition from BDs of 4-6 XYBs to LP*s of Al atoms dominates the peak located at visible

Figure 6E compares the absorption spectrum of Be12O12 nanocage with the average

spectrum of complex related to this nanocage. The TD-DFT calculation shows that the spectrum of Be12O12 have one intense peak in 140-150 nm area. As shown in Table S12, this peak is due to electronic transition from LPs of O atoms to Rydberg-type orbitals (RY*) of Be atoms. The adsorption of sulfur mustard on the surface of the nanocage removes the intense peak of the spectrum of the nanocage and replaces it with several very lower intense

ACCEPTED MANUSCRIPT peaks in longer wavelengths (140-200 nm). As seen in Figure S19, the UV spectra of all geometries of this complex are similar, but a labeled geometry has a major contribution in the average UV spectrum of the complex. The precise investigation of the spectrum of a labeled geometry shows that a variety of different types of electron transitions such as: LPs of Cl

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atoms of sulfur mustard
BD*s of bonds of the sulfur mustard, LPs of O of the nanocage
RY*s of Be atoms of the nanocage, LPs of O atoms of the nanocage
BD*s of bonds of the sulfur mustard, and BD of Be-S bond
BD*s of bonds of the sulfur mustard form these

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peaks. However, the adsorption of sulfur mustard makes an appreciable change in UV spectrum of the Be12O12 nanocage, but the observation of the spectra of the Be12O12 nanocage

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and related complexes is very difficult experimentally, because peaks of present solvents appear in about 200 nm and lower wave lengths and therefore can cutoff the peaks of the nanocage and related complexes. Thus, the Be12O12 nanocage cannot be used as a suitable UV sensor for sulfur mustard.

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According to Figure 6F, the UV spectrum of B12N12 nanocage has a sharply intense peak in 160-180 nm and a widely peak with low intensity in a longer wavelength. The electronic transitions from BDs of 6-6 XYBs to the BD*s of 6-6 XYBs form these peaks.

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Similar to Be12O12, the intense peak of the UV spectrum of the B12N12 nanocage is removed

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after the adsorption of sulfur mustard on its surface. Also, the adsorption of sulfur mustard on the surface of the nanocage considerably increases the intensity of wide peak placed at longer wavelength. As depicted in Figure S20, the average UV spectrum of sulfur mustard-B12N12 is dominated with a and f labeled geometries. The spectra of both geometries have a wide peak in 170-200 nm area which intensity of this peak in f labeled geometry is more than a labeled geometry. As seen in Table S13, a variety of type of the electron transitions play a role in the main peak in the spectrum of a labeled geometry whereas the electron transition from BDs of 4-6 XYBs of the nanocage to BD*s of bonds of sulfur mustard is responsible for appearance

ACCEPTED MANUSCRIPT of the main peak in the spectrum of the f labeled geometry. Given that the peaks in spectra of the B12N12 nanocage and related complexes are located in wave lengths less than 200 nm, the experimental observation of these peaks is difficult and therefore, this nanocage is not suitable for UV sensing of sulfur mustard.

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The average UV spectrum of the sulfur mustard-Mg12O12 complex is compared with the spectrum of the isolated nanocage in Figure 6G. The spectrum of the Mg12O12 nanocage has an intense peak at 240-280 nm region which is due to electronic transition from LPs of O

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atoms to the BD*s of 6-6 XYBs. The adsorption of sulfur mustard on the surface of the Mg12O12 has not considerably effect on the spectrum of the nanocage. The c labeled geometry

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has the most contribution in the average spectrum. As shown in Table S14, the electronic transition from LPs of O atoms to BD*s of 6-6 XYBs is still main reason for the appearance of the peak at the spectrum of the geometry. However, the electronic transition from BDs of 6-6 XYBs to BD*s of 6-6 XYBs and electron transition from the LP of S atom of sulfur

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mustard to BD*s of 6-6 XYBs contribute to it. Therefore, the Mg12O12 nanocage is not useful

Conclusion

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for UV detecting of the sulfur mustard.

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In this work, the ability of C24, C12Si12, Al12N12, Al12P12, Be12O12, B12N12 and Mg12O12 nanocages for adsorbing and detecting of sulfur mustard, a chemical warfare agent, was investigated using B3LYP-D3 method accompanied with 6-31g(d) basis set. It is found that the best adsorbent for sulfur mustard is Al12N12 among the selected nanocages. Also, C12Si12 and Mg12O12 are useful for adsorbing this chemical agent. The DOS study of adsorption of sulfur mustard on the surface of these nanocages showed that the electroconductivity of B12N12 and Be12O12 considerably increases after adsorption. Also, the adsorption of sulfur mustard on the surface of the nanocages makes an acceptable change in

ACCEPTED MANUSCRIPT the UV spectrum of C24, C12Si12, Al12P12, Be12O12, and B12N12. Among them, the peaks of Be12O12, B12N12 and related complexes appear at 140-200 nm region which their experimental observation is difficult, thus these nanocages are not suitable for sensing of sulfur mustard. Also, the adsorption of sulfur mustard on the surface of the C12Si12 is strong

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and recycling of this nanocage is difficult. Therefore, the use of the C12Si12 nanocage as sensor for sulfur mustard is not sensible. Based on what was mentioned, the Be12O12, and B12N12 nanocages can use as electroconductive sensors and the C24 and Al12P12 is suitable as

Electronic Supplementary Information

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UV sensor for the sulfur mustard.

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The electronic supplementary information includes:

1) Table S1-S21 2) Figure S1-S21 3) The coordinates of the nanocages and complexes which studied by CMO analysis References

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ACCEPTED MANUSCRIPT Tables

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Table 1. the most important values of Vmax and Vmin of sulfur mustard and nanocages structure Vmax Vmin Sulfur mustard 26.93 -13.43 Al12N12 54.50 -27.35 Al12P12 51.78 -9.74 B12N12 28.65 -13.96 Be12O12 54.50 -19.25 Mg12O12 110.05 -34.79 C12Si12 31.48 -19.24 C24 12.43 -3.15

ACCEPTED MANUSCRIPT Table 2. The calculated values of Eads, Eint, Edef and ∆E0 of adsorption of sulfur mustard on the surface of nanoages at B3LYP-D3/6-31G(d) level of theory. (the calculated values at B3LYP-D3/6-31++G(d, p) were reported in parentheses) Eint (kcal/mol)

Edef (kcal/mol)

-6.026 (-5.924) -1.649 (-1.634) -3.968 (-3.717) -3.960 (-3.668) -5.522 (-5.205) -4.353 (-4.343)

0.053 (0.000) 0.000 (0.000) 0.000 (0.000) 0.000 (0.000) 0.344 (0.000) 0.000 (0.000)

-27.821 (-27.682) -18.843 (-18.516) -13.430 (-13.163) -16.607 (-16.307) -12.474 (-12.217) -26.491 (-26.312)

5.252 (5.219) 2.304 (2.213) 1.749 (1.679) 2.509 (2.443) 1.727 (1.633) 4.895 (4.870)

Sulfur mustard-C24

c d e f

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Sulfur mustard-C12Si12 -22.569 a* (-22.462) -16.538 b (-16.303) -11.680 c (-11.484) -14.098 d (-13.864) -10.747 e (-10.585) -21.596 f (-21.443)

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Sulfur mustard-Al12N12 -23.780 a (-23.594) -25.492 b* (-25.206) -23.937 c (-23.579) -22.906 d (-22.721)

-5.268 -1.292

-3.448

-3.429

-4.654

-3.734

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b

-5.973 (-5.924) -1.649 (-1.634) -3.968 (-3.717) -3.960 (-3.668) -5.178 (-5.205) -4.353 (-4.343)

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a*

∆E0 (kcal/mol)

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Eads (kcal/mol)

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Structure

-27.578 (-27.408) -33.364 (-32.882) -28.528 (-28.112) -26.794 (-26.624)

3.799 (3.814) 7.872 (7.676) 4.591 (4.532) 3.888 (3.903)

-21.183 -15.513

-10.948

-12.916 -10.125 -20.266

-22.745 -24.353 -23.000 -21.752

ACCEPTED MANUSCRIPT Continuance of Table 2.

Sulfur mustard-Al12P12 -18.891 a (-18.505) -10.849 b (-10.500) -10.885 c (-10.519) -19.033 d* (-18.719) -17.231 e (-16.512)

-23.325 (-22.828) -13.518 (-13.047) -13.647 (-13.141) -25.505 (-25.073) -21.915 (-21.049)

4.434 (4.323) 2.669 (2.547) 2.762 (2.623) 6.471 (6.354) 4.684 (4.537)

Sulfur mustard-Be12O12 -16.124 a* (-16.133) -14.991 b (-14.790) -13.976 c (-13.731) -10.775 d (-10.606) -13.598 e (-13.508) -11.099 f (-10.925)

-22.102 (-22.063) -20.090 (-19.751) -18.822 (-18.471) -13.658 (-13.437) -17.862 (-17.667) -13.794 (-13.542)

5.978 (5.930) 5.098 (4.961) 4.847 (4.740) 2.883 (2.830) 4.263 (4.158) 2.694 (2.617)

-26.144 (-27.024) -9.219 (-9.122) -6.255 (-6.026) -8.477 (-8.365) -6.266 (-6.167) -24.376 (-25.245)

13.774 (13.527) 0.667 (0.601) 0.431 (0.431) 0.873 (0.843) 0.541 (0.518) 12.254 (11.988)

-17.869

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Sulfur mustard-B12N12 -12.370 a* (-13.497) -8.553 b (-8.521) -5.823 c (-5.596) -7.605 d (-7.522) -5.725 e (-5.649) -12.122 f (-13.257)

∆E0 (kcal/mol)

-10.380

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Edef (kcal/mol)

Eads (kcal/mol)

-10.341

-18.047

-16.213

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Eint (kcal/mol)

Structure

-14.899 -14.121

-13.102 -9.911 -12.564 -10.149

-11.226 -7.906 -5.188 -7.110 -5.275 -11.181

ACCEPTED MANUSCRIPT Continuance of Table 2.

Sulfur mustard-Mg12O12 -22.724 a (-22.844) -21.869 b (-21.918) -22.927 c* (-22.981) -19.067 d (-18.941) -18.612 e (-18.946)

Eint (kcal/mol)

Edef (kcal/mol)

-28.252 (-28.163) -24.794 (-24.728) -25.492 (-25.415) -23.824 (-23.578) -20.022 (-20.295)

5.528 (5.319) 2.925 (2.810) 2.566 (2.435) 4.758 (4.637) 1.411 (1.349)

-21.731

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*The most stable geometries of each complex

∆E0 (kcal/mol)

-21.071

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Eads (kcal/mol)

-22.187

-18.113

-17.863

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Structure

ACCEPTED MANUSCRIPT Table 3. The QTAIM analysis of interaction of sulfur mustard with the surface of nanocages in the most stable geometries G

V

H

|V|/G

0.0192 0.0177 0.0185 0.0184 0.0149 0.0193

0.0038 0.0035 0.0036 0.0036 0.0030 0.0038

-0.0027 -0.0026 -0.0026 -0.0026 -0.0022 -0.0027

0.0010 0.0009 0.0010 0.0010 0.0007 0.0010

0.7257 0.7324 0.7169 0.7159 0.7509 0.7259

Sulfur Mustard-C12Si12 (a) S-Si 0.0645 0.0126 Hβ -C 0.0134 0.0370

0.0378 0.0084

-0.0725 -0.0075

-0.0347 0.0009

1.9165 0.8974

Sulfur Mustard-Al12N12 (b) S-Al 0.0365 0.0999 Hβ -N 0.0143 0.0438 Cl-Al 0.0240 0.0641 Hα -N 0.0131 0.0408

0.0320 0.0100 0.0188 0.0092

-0.0390 -0.0091 -0.0216 -0.0083

-0.0070 0.0009 -0.0028 0.0010

1.2188 0.9083 1.1489 0.8947

Sulfur Mustard-Al12P12 (d) Hβ -P 0.0065 0.0205 Hβ -P 0.0054 0.0170 S-Al 0.0379 0.0857 Hα -P 0.0068 0.0209 Hβ -P 0.0058 0.0176

0.0040 0.0032 0.0302 0.0041 0.0034

-0.0028 -0.0022 -0.0390 -0.0030 -0.0024

0.0011 0.0010 -0.0088 0.0011 0.0010

0.7135 0.6871 1.2912 0.7240 0.6987

Sulfur Mustard-Be12O12 (a) S-Be 0.0376 0.1312 Hβ -O 0.0159 0.0505

0.0401 0.0124

-0.0475 -0.0122

-0.0073 0.0002

1.1828 0.9829

0.0406

-0.1041

-0.0636

2.5671

0.0098

-0.0090

0.0008

0.9212

0.0168 0.0158 0.0107 0.0169

-0.0141 -0.0168 -0.0103 -0.0141

0.0028 -0.0009 0.0004 0.0027

0.8348 1.0582 0.9618 0.8377

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-./

Structure ρ Sulfur Mustard-C24 (a) Cl-C 0.0063 Hβ-C 0.0061 Hα-C 0.0060 Hα-C 0.0059 Hβ-C 0.0045 Cl-C 0.0063

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Sulfur Mustard-B12N12 (a) 0.0850

Hβ -N

0.0141

0.0920 0.0422

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S-B

Sulfur Mustard-Mg12O12 (c) Cl-Mg 0.0161 0.0785 Hα-O 0.0212 0.0596 Hβ-O 0.0140 0.0444 Cl-Mg 0.0161 0.0784

ACCEPTED MANUSCRIPT

-5.649

C12Si12

-2.436 -2.299 -2.518 -2.344 -2.530 -2.435

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Sulfur mustard-C12Si12 -5.704 a* -5.587 b -5.778 c -5.613 d -5.786 e -5.714 f

-3.821

1.828

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C24

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Table 4. The energies of HOMO and LUMO, the energy gap (Eg) and charge transfer (Q) for adsorption of sulfur mustard on the surface of nanocages. The negative value of charge means that there is electron charge transfer from the sulfur mustard to nanocage. Q(e) Structure ƐHOMO(eV) ƐLUMO(eV) Eg (eV) Sulfur mustard-C24 -5.701 -3.925 1.776 -0.010 a* -5.581 -3.758 1.823 0.000 b -5.768 -3.935 1.833 0.002 c -5.755 -3.944 1.811 -0.006 d -5.695 -3.864 1.831 -0.020 e -5.750 -3.917 1.834 -0.020 f 0.000

3.268 3.289 3.260 3.269 3.256 3.279

-0.360 -0.390 -0.240 -0.340 -0.240 -0.350

-2.796

3.254

0.000

Sulfur mustard-Al12N12 -6.255 a -6.041 b* -5.997 c -6.207 d

-2.266 -2.006 -2.037 -2.247

3.989 4.035 3.960 3.960

-0.210 -0.340 -0.320 -0.230

-6.478

-2.522

3.957

0.000

Sulfur mustard- Al12P12 -6.497 a -6.524 b -6.524 c -6.483 d* -6.363 e

-3.117 -3.138 -3.144 -3.132 -2.943

3.380 3.386 3.380 3.351 3.420

-0.240 -0.180 -0.190 -0.250 -0.310

-3.362

3.387

0.000

EP

-6.051

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Al12N12

Al12P12

-6.749

-8.542

B12N12

-0.773 -0.777 -0.908 -0.856 -0.802 -0.800

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Sulfur mustard-B12N12 -7.199 a* -6.841 b -6.793 c -6.824 d -6.857 e -7.190 f

-0.254

7.334 6.561 6.555 6.382 6.315 6.375

-0.240 -0.320 -0.300 -0.180 -0.210 -0.190

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Be12O12

-0.448 -0.479 -0.491 -0.596 -0.593 -0.600

8.288

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Continuance of Table 4. Sulfur mustard-Be12O12 -7.783 a* -7.040 b -7.046 c -6.978 d -6.907 e -6.975 f

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0.000

6.427 6.064 5.885 5.968 6.055 6.390

-0.500 -0.120 -0.030 -0.110 -0.100 -0.490

-0.864

6.839

0.000

Sulfur mustard-Mg12O12 -6.397 a -6.282 b -6.297 c* -6.368 d -6.518 e

-1.497 -1.454 -1.442 -1.492 -1.622

4.901 4.828 4.856 4.876 4.896

-0.160 -0.160 -0.170 -0.150 -0.090

-6.563 -1.693 Mg12O12 *The most stable geometries of each complex

4.870

0.000

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-7.703

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Figures

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Figure 1. The most stable structure of sulfur mustard accompanied with its MEP

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A)

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B)

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Figure 2. The most stable structure of A) Al12N12 and B) C24 accompanied with their MEPs

ACCEPTED MANUSCRIPT B) Sulfur Mustard-C12Si12 (a)

C) Sulfur Mustard-Al12N12 (b)

D) Sulfur Mustard-Al12P12 (d)

F) Sulfur Mustard-B12N12 (a)

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E) Sulfur Mustard-Be12O12 (a)

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A) Sulfur Mustard-C24 (a)

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G) Sulfur Mustard-Mg12O12 (c)

Figure 3. The stable geometry relative to the adsorption of sulfur mustard on the surface of each complex

ACCEPTED MANUSCRIPT B) Sulfur Mustard-C12Si12 (a)

C) Sulfur Mustard-Al12N12 (b)

D) Sulfur Mustard-Al12P12 (d)

F) Sulfur Mustard-B12N12 (a)

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E) Sulfur Mustard-Be12O12 (a)

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A) Sulfur Mustard-C24 (a)

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G) Sulfur Mustard-Mg12O12 (c)

Figure 4. The difference electron density maps (0.0008 e par a.u) for the most stable structure of complex for each nanocage

C24

B)Sulfur mustard-C12Si12 (a)

C12S12

Al12N12

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C)Sulfur mustard-Al12N12 (b)

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A)Sulfur mustard-C24 (a)

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D)Sulfur mustard-Al12P12 (b)

Al12P12

ACCEPTED MANUSCRIPT Be12O12

B12N12

Mg12O12

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G)Sulfur mustard-Mg12O12 (c)

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F)Sulfur mustard-B12N12 (a)

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E)Sulfur mustard-B12O12 (a)

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Figure 5. The DOS of the structures for the stable complexes compared with its corresponding nanocage

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A)Sulfur mustard-C24

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C)Sulfur mustard-Al12N12

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B) Sulfur mustard-C12Si12

D) Sulfur mustard-Al12P12

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E) Sulfur mustard -Be12O12

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G) Sulfur mustard-Mg12O12

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F) Sulfur mustard-B12N12

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Figure 6. The Boltzmann average spectra of the complexes compared with the spectrum of its corresponding isolated nanocage

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The interaction of sulfur mustard with some nanocages were studied.
The Al12N12, C12Si12 and Mg12O12 are useful for the adsorption of the sulfur mustard.

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The Al12P12, Be12O12 and B12N12 nanocages are useful sensors for this chemical agent.