Adsorption behaviour of chronic blistering agents on graphdiyne; excellent correlation among SAPT, reduced density gradient (RDG) and QTAIM analyses

• Published in: Journal of molecular liquids 2020-10, Vol.316, p.113860, Article 113860
• Main Authors: Khan, Sidra, Sajid, Hasnain, Ayub, Khurshid, Mahmood, Tariq
• Format: Article
• Language: English
• Subjects: Blistering agents; Graphdiyne; QTAIM; Reduced density gradient; Symmetry adopted perturbation
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2020.113860

The chemical warfare agents (CWAs) are highly toxic for living systems and environment. These diverse effects of CWAs, especially blistering agents, need the development of highly selective sensors for their rapid and effective detection. Herein, by using density functional theory calculations, we explained the adsorption of nitrogen (NM) and sulphur mustard (SM) blistering agents on graphdiyne (GDY) sheet. The calculated adsorption energies illustrate the physisorption of blistering (SM & NM) agents on the graphdiyne surface. The symmetry adopted perturbation theory (SAPT) analysis predicts that the dispersion is a dominating component of interaction energy. Reduced density gradient (RDG) and quantum theory of atoms in molecules (QTAIM) analyses are performed to justify the nature of interactions. Based on QTAIM analysis, the interaction energies between graphdiyne and blistering agents are noncovalent in nature. Furthermore, RDG results reveals that the van der Waals interactions i.e., dispersion forces dominate in the complexes. The %sensitivity and average energy gap variations are illustrated by HOMO-LUMO gaps. The detection ability of graphdiyne is further studied using UV–Vis analysis, NBO charge transfer and density of state analysis. These properties depict the appreciable sensitivity of graphdiyne towards blistering agents (SM and NM). We believe that the results of this study are fruitful for experimentalist to design highly sensitive CWAs sensors using graphdiyne sheet. [Display omitted] •The adsorption of blistering agents on GDY is studied by ωB97XD/6-31+G(d,p) method of DFT.•Adsorption behaviour is elucidated by SAPT, RDG and QTAIM analyses.•The dispersion forces dominate between BA-GDY complexes.•This study shows that GDY sheet has high sensitivity towards blistering agents.