Adsorption of phosgene on Al12N12 nanocluster: Quantum chemical study

A Amiri ¹ ( Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran )
Reza Ghiasi ² ( East Tehran branch of Islamic azad university )
Karim Zare ³ ( Science Department, Science and Research Branch, Islamic Azad University, Tehran, Iran )
Reza Fazaeli ⁴ ( Department of Chemistry, Faculty of Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran )

Submited date : 2020-11-10 Accepted date : 2021-02-15

Keywords:

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Adsorption of phosgene on Al12N12 nanocluster: Quantum chemical study  

 

Asma Amiri1, Reza Ghiasi*,2, Karim Zare1, Reza Fazaeli3

 

1 Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran

 2 Department of Chemistry, East Tehran Branch, Islamic Azad University, Tehran, Iran

E-mail to: [e-mail], [e-mail], Tel/Fax Number: [phone]

3 Department of chemistry, South Tehran Branch, Islamic Azad University, Tehran, Iran

 

Abstract:

This study investigated the adsorption of phosgene gas on Al12N12 nanocluster with using CAM-B3LYP functional. Six possible isomers of the interaction between Al12N12 nanocluster and phosgene were considered. The interactions between nanocluster and phosgene were examined through energy decomposition analysis (EDA). Charge transfer between fragments were illustrated with electrophilicity-based charge transfer (ECT). Thermodynamics parameters of the interaction between of nanocluster and phosgene gas were calculated. The temperature and pressure effects on the thermodynamic parameters were illustrated.

 

Keywords: Al12N12 nanocluster, phosgene, thermodynamics parameters, temperature effect, pressure effect.

 

Introduction

Phosgene (COCl2) and its derivatives are one of the main classes of air pollutants. In the natural world, it is employed in pesticides, dyes and pharmaceuticals process. Phosgene was first used in World War I as a chemical weapon. The mortal dose for a human being is 2 ppm [1]. Furthermore, it is employed in the industrial synthesis many organic compounds, such as isocyanates, polyurethane, poly carbamates, and other materials [2]. Monitoring and controlling the amount of pollutants is main issue for our safety and health for modern society [3-5] . Many considerations have been focused on the progress of suitable gas-sensitive materials for hazardous chemical vapors detection. Air pollution is alteration in the physical, chemical and biological properties of air that causes effects on human health and the surroundings [6]. Research shows that using nanostructures, due to enhancing ecological pollution, the prevalence of war diseases for preparation of gas sensor is considered [7].

Attentions to the nanostructures such as fullerene hollow nanocages of elements other than carbon have increased because of due to their exclusive electronic and optical properties [8-11]. Group III-V nitrides are between most favorable nanocages [12, 13]. In this family, useful applications have reported for AlN nanoclusters. These nanoclusters have revealed thermodynamic stability, and high thermal conductivity and low electron affinity [14]. The investigation of aluminum nitride nanoclusters (n=2-41) explored that Al12N12 nanocluster is energetically the most stable one, and can be reflected as an appropriated nanocluster [15]. Al12N12 nanocluster has been shown interesting applications in gas sensing and hydrogen storage [16]. Various computational investigations have been reported about adsorption of different molecules on the AlN nanocluster [17-23].

This theoretical study examined the interaction between Al12N12 nanocluster with phosgene. This work was done employing quantum chemical calculations, in which it is indeed an advantage of performing such calculations to provide insightful information at the lowest atomic scales especially for investigating the complicated nanostructures [24-28]. Variations in the structural parameters, frontier orbital energies and electron transfer between fragments were illustrated. Thermodynamics of this interaction was investigated and the temperature and pressure effects on the thermodynamic parameters were illustrated.

 

Computational Methods

Optimization and vibrational analysis were done with Gaussian 09 software package [29]. The standard 6-311G(d,p) basis set [30-33] were considered for the elements, respectively. The geometries of the compound were optimized by the CAM-B3LYP functional. This functional is Handy and coworkers’ long range corrected version of B3LYP using the Coulomb-attenuating method [34].  The identities of the optimized structures as an energy minimum were confirmed by vibrational analysis.

Energy decomposition analysis (EDA) was studied for illustration of the bonding interactions between the Al12N12 and phosgene [35-37]. The interaction energy (DEint) between the two fragments was evaluated as DEpolar  + DEels + DEEx. Where DEpolar, DEels and DEEx are the electron density polarization term (the induction term), the electrostatic interaction and the exchange repulsion terms, respectively. EDA calcuations were  performed on the optimized geometry with the used level of theory for optimization using Multiwfn 3.7 software package [38, 39]. The percentage contributions of atomic orbitals in the frontier orbitals were calculated using GaussSum 3.0 software package [40].

 

 

Results and discussion

1.       Energetic aspects.

The various isomers of the adsorption of COCl2 gas on the Al12N12 nanocluster are presented in Figure 1. The absolute energy and relative energy values of these isomers are calculated at the CAM-B3LYP/6-311G(d,p) level of theory (Table 1). It can found, E-isomer is most stable isomer.

Stability of Al12N12…COCl2 isomers is evaluated by cohesive energy (Ecoh)

Ecoh = EAl12N12…COCl2 – (12 EAl + 12 EN + EC + EO + 2 ECl)

Where, EAl12N12…COCl2 is energy of complex, EAl, EN, EC, EO and ECl are energy of aluminum, nitrogen, carbon, oxygen and chlorine atoms, respectively. The calculated Ecoh values show that E-isomer is most stable isomers (Table 1). It can be found, pure Al12N12 nanocluster (Ecoh = -279.75 eV) is more stable than metal doped Al12N12 nanocluster.

 

2.       Energy decomposition analysis (EDA)

Energy decomposition analysis (EDA) was used to clarify the nature of the Al…Cl chemical bond in the E-isomer of Al12N12…COCl2 molecule. The EDA calculations results of E-isomer show that the interaction energy between Al12N12 and COCl2 are calculated as -183.46558 kcal/mol. Moreover, while the polarization energies equal to -457.81 kcal/mol stabilized Al12N12… COCl2 complex, the sum of the electrostatic and exchanging energies destabilized the Al12N12… COCl2 complex by 274.30 kcal/mol in E-isomer.

 

3.       Bond distances.

The most important bond distance between atoms in the different isomers of Al12N12…COCl2 molecule are shown in Figure 1.  It can be observed, the shortest distances values between Al and Cl atoms in the E-isomer of Al12N12…COCl2 molecule is 2.131 Å. On the other hand, the shortest distances values between N and Cl atom is 1.785 Å.

 

4.       Thermodynamic parameters

Free energy enthalpy and entropy changes values (DG, DH and DS, respectively) of Al12N12…COCl2 complex formation are calculated in the basis of the following reactions:

 

Al12N12 + COCl2 ® Al12N12…COCl2;         DX =X(Al12N12…COCl2) – X(Al12N12) - X(COCl2); X=G, H, S

 

The calculated DG, DH and DS values of this reaction in the 298 K and 1atm pressure are -26.40 kcal/mol, -31.35 kcal/mol and -16.59 cal/mol.K, respectively. The negative DG and DH values of the E-isomer of Al12N12…COCl2 complex formation reveals that this reaction is spontaneous and exothermic, respectively. The negative DS values of these reactions are logical. Because, formation of the one molecules after interaction between two molecules decrease entropy of reaction.

Formation constant values (K) of the Al12N12…COCl2 complex is calculated by the following formula:

 

 

 

The calculated K value is 2.32 ´ 1019.  

The effect of pressure on the thermodynamic properties are explored. The temperature and pressure-dependent behaviors of this reaction is investigated in a wide range of conditions (T = 100–1000 K and P = 0.1–1000 atm (Tables 2 and 3).

During the adsorption process, the enhancement of DG, DH and DS are observed distinctly along with the increasing of the temperature. Therefore, the adsorption occurs easily under lower temperature. There are good linear correlations between of DG and DH with temperature:

 

DG = 0.0137 T - 30.838;                R² = 0.9855

DH = 0.0058 T - 33.245;                R² = 0.9794

But, there is not good linear correlations between DS values and temperature:

 

DS = 0.0155 T - 23.136                R² = 0.796

The temperature dependency of DS values is fitted by quadratic equation:

DS = -3´ 10-5 T2 + 0.0459 T - 29.214;                R² = 0.9585

 

During the adsorption process, the decreasing of DG values are observed distinctly along with the increasing of the pressure. Therefore, the adsorption occurs easily under higher pressure. There are good linear correlations between of DG with logarithm of pressure:

 

DG = -1.3642 log (P) - 26.404;        R² = 1

 

The variation of DS during the adsorption increases distinctly along with the enhancement of pressure. There are good linear correlations between of DS with logarithm of pressure:

DS = 4.5757 log (P) - 16.59;                R² = 1

5.       Molecular orbital analysis

The frontier orbitals energy, the corresponding HOMO–LUMO energy gaps, hardness, chemical potential values of Al12N12…COCl2, Al12N12 and COCl2 molecules are given in Table 4. Plots of frontier orbitals of E-isomer of Al12N12…phosgene molecule are presented in Figure 2. Comparison of the frontier orbitals energy values in the E-isomer of Al12N12… COCl2 with Al12N12 nanocluster shows COCl2 adsorption meaningfully destabilizes and stabilizes the HOMO and LUMO levels of Al12N12 nanocluster, respectively. However, it seems that the COCl2 share electron with the LUMO level because of its strong stabilization. On the other hand, comparison of the HOMO-LUMO gap value in the E-isomer of Al12N12… COCl2 with Al12N12 nanocluster indicates COCl2 adsorption meaningfully increases this value. Therefore, we believe that the Al12N12 may be a suitable nanoscale carrier for COCl2 gas.

 

6.       Electrophilicity-based charge transfer (ECT)

Now, electrophilicity-based charge transfer (ECT) of E-isomer of Al12N12… COCl2 molecule is calculated. ECT is defined as the difference between DNmax values of interacting molecules [41]:

 

ECT = DNmax(COCl2) - DNmax(Al12N12)

 

In this equation DNmax is defined as:

 

h and m are global hardness and chemical potential. They are defined as global reactivity descriptors [42-45] and determined on the basis of Koopman’s theorem [46]. This values for Al12N12, COCl2 and E-isomer of Al12N12… COCl2 are calculated by the following equations: 

 

 

 

 

The calculated DNmax value is 1.37. The positive value of ECT reveal charge flow from Al12N12 to COCl2. 

 

Conclusion:

Computational investigation of the adsorption behavior of phosgene on Al12N12 nanocluster revealed E-isomer was most stable isomer in between the studied isomers. The calculated Ecoh values showed that E-isomer was most stable isomers. The larger HOMO-LUMO gap value in the E-isomer of Al12N12… COCl2 rather than Al12N12 nanocluster showed that COCl2 adsorption meaningfully increase this value. Therefore, we believe that the Al12N12 may be a suitable nanoscale carrier for COCl2 gas. The positive value of ECT revealed charge flow from Al12N12 to COCl2 gas. Thermodynamics analysis showed easy adsorption under lower temperature and higher pressure.

 

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