Inclusive DFT insight into sensing mechanism of cyclotetrapyrole towards lung irritants.

The development of smart sensing devices for toxic analytes detection especially lung irritants is much essential. The cyclic conducting polymers having infinite π-conjugation are proved to be highly sensitive for toxic analytes. Herein, by using the DFT approach, we investigated the sensing mechanism of cyclotetrapyrole (CTPy) for accurate detection of phosgene, diphosgene, chloropicrin and chlorine at the B3LYP-D3/6-31 + G (d, p) level. The calculated interaction energies show the physisorption of analytes over the CTPy surface. Natural bond orbital (NBO) and charge decomposition (CDA) analyses predict charge transfer interactions in the complexes. The reduced density gradient (RDG) approach reveals that hydrogen bonding interactions dominate in the complexes. The sensitivity of CTPy towards lung irritants is further illustrated by the reduction in HOMO-LUMO energy gaps, red shifting of [Formula: see text] in UV-Visible spectra. Density of state (DOS) analysis affirm that enhanced conductivity upon complexation is due to the origination of new energy states in occupied and virtual orbitals nearer to the Fermi level. Moreover, PDOS spectra show that CTPy primarily contributes to the energy of HOMO. The outcome of the current study depicts appreciable sensitivity of CTPy towards lung irritants. Moreover, the competing role of naturally occurring atmospheric water is also investigated. We believe that the upshot of the current findings and their forecasts will provide useful guidelines for an experimentalist to design highly sensitive sensors for toxic analytes using CTPy. HIGHLIGHTS: • The highest QNBO transfer towards the analyte (- 0.121) is seen in the chlorine@CTPy complex. • The highest reduction in Eg (61%) between occupied and virtual orbitals is noticed in chlorine@CTPy. • The orbital overlap results in a 41% red shifting of [Formula: see text] in chlorine@CTPy. • Cyclotetrapyrole is highly sensitive for chlorine.