Computational Study of Pristine, Al‐ and P‐Doped B 12 N 12 Nanocages for BrCN Adsorption and Detection under Electrostatic Fields Using Density Functional Theory, Time‐Dependent‐Density Functional Theory, and Reduced Density Gradient

This study presents a comprehensive computational investigation of the adsorption and sensing potential of pristine and doped B 12 N 12 nanocages B 12 N 12 , AlB 11 N 12 , and B 12 N 11 P toward cyanogen bromide (BrCN), a highly toxic gas. Equilibrium structures of the BrCN complexes are optimized at the ω B97XD/6‐31 G (d, p) level, and adsorption energies, thermodynamic parameters (Δ H , Δ G ), and electronic descriptors are calculated. Interaction analyses are performed using atoms in molecules, reduced density gradient, molecular electrostatic potential, and electron localization function approaches. The effects of solvents, nonlinear optical properties, and UV–visible spectra are examined under neutral conditions and external static electric fields (SEF, z + 0.01 to z + 0.04 au). Results reveal that BrCN adsorption is strongest on AlB 11 N 12 , exhibiting favorable thermodynamics in both gas and aqueous phases, highlighting its potential for realistic sensing applications. While increasing SEF generally reduces adsorption energies, the pristine B 12 N 12 complex shows an exception. Reactivity and conductivity analyses indicate a superior electronic response for AlB 11 N 12 , with noncovalent interactions, primarily van der Waals forces, governing the binding. Overall, AlB 11 N 12 is identified as a promising candidate for the design of selective and sensitive BrCN gas sensors.