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A hexagonal outlined porous cladding with vacant core photonic crystal fibre (HOPC‐VC‐PCF) sensor using Zeonex has been presented, which can detect cyanides at the THz regime. Cyanides are incredibly lethal chemicals to humans as they can rapidly cause impairment or even death; such harmful substances must be identified precisely. The proposed model has been analysed at a broad spectrum of THz regimes for three different analytes, and the numerical investigation is performed using the Finite element method (FEM). Simulation results exhibit that at optimum design parameters, extremely high sensitivity of 99.75%, negligible confinement loss of 0.5 × 10−13 cm−1, extremely low and flat dispersion of 0.12 ps THz/cm, and other excellent features were obtained. The performance analysis and the design methodology have been depicted in detail. Due to the simplistic design, fabrication of the model is easily achievable by current technology. The remarkable sensing capabilities will not only make it suited in chemicals analysis but also will play vital roles in other applications as well.

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