An accurate comparative theoretical study of the interaction of furan, pyrrole, and thiophene with various gaseous analytes.

An accurate comparison of the interaction of furan, pyrrole, and thiophene with different gaseous analytes is vital not only for understanding the sensing mechanism of corresponding polymers but also for rational design of new materials. In the present study, DFT calculations at (M05-2X/Aug-cc-PVDZ) have been performed to investigate the interaction behavior of furan, pyrrole, and thiophene (as models for their corresponding polymers) with different analytes (NH3, CO2, CO, N2H4, HCN, H2O2, H2S, CH4, CH3OH, SO2, SO3, H2O). The interaction of heterocycles with analytes is illustrated by changes in geometric, energetic, and electronic properties. SAPT calculations were performed for energy decomposition analysis to study the contribution of non-covalent components of the total interaction energy for each complex. Analysis of energetic and electronic properties reveals that all heterocycles are highly sensitive to SO3. The results suggest that sensing ability of polypyrrole is higher than polyfuran and polythiophene for all analytes. Graphical abstract SAPT0 energies (kcal mol-1) of furan, pyrrole, and thiophene with various gaseous analytesᅟ.