Sensing of toxic Lewisite (L1, L2, and L3) molecules by graphdiyne nanoflake using density functional theory calculations and quantum theory of atoms in molecule analysis

• Published in: Journal of physical organic chemistry 2021-05, Vol.34 (5), p.n/a
• Main Authors: Khan, Sidra, Sajid, Hasnain, Ayub, Khurshid, Mahmood, Tariq
• Format: Article
• Language: English
• Subjects: adsorption; Charge transfer; Chemical warfare; Density functional theory; Dichlorides; Doppler effect; Energy gap; graphdiyne nanoflake; Molecular orbitals; Perturbation theory; Quantum theory; Red shift; Sensitivity
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.4181

Promising sensor applications of graphdiyne for various gases and toxic molecules have extensively been studied; however, similar studies for the detection of chemical warfare agents (CWA) are not reported. Here, we report the adsorption of Lewisites (L1, L2, and L3), on graphdiyne nanoflake (GDY) using density functional theory (DFT) ωB97XD/6‐31+G (d,p) method. Our results show that Lewisite molecules are preferably physiosorbed at the triangular portion of GDY nanoflake. In particular, the binding of L3 (3‐chlorovinyl arsine) on GDY nanoflake is thermodynamically favorable than L1 (1‐chlorovinylarsonous dichloride) and L2 (2‐chlorovinylarsonous chloride). Symmetry adopted perturbation theory (SAPT0) analysis reveals that the least contribution of repulsive exchange component is present in case of L2@GDY complex. Further, the smallest HOMO‐LUMO energy gap, appreciable charge transfer (NBO), and largest red shift in ultraviolet‐visible (UV‐Vis) spectrum are also in accord with the higher %sensitivity of graphdiyne toward L2. Quantum theory of atom in molecule (QTAIM) analysis is performed to get insight into the noncovalent interactions. Therefore, it is predicted that the sensitivity of GDY nanoflake is potentially high for Lewisite especially for L2. The sensor applications of graphdiyne nanoflake toward Lewisite molecules are not explored yet. Herein, we study the adsorption behaviour of three different Lewisites on graphdiyne nanoflake within the density function theory framework. 2‐chlorovinylarsonous chloride (L2) binds more favorably than 1‐chlorovinylarsonous dichloride (L1) and 3‐chlorovinyl arsine (L3).