A new subseries of bands was observed on the previously reported series of peaks forming the structure of the ν1(HF) band of the HCN⋯HF complex. This is assigned to hot transitions from the excited states of the hydrogen bond stretching ν4 and hydrogen bond bending ν1 modes. The obtained spectra of HCN/HF/Xe mixtures with Xe density increasing up to 8.2 amagat suggest resonance interactions between 2ν7 and ν4 and/or ν1 + 2ν7 and ν1 + ν4 vibrational levels of the HCN⋯HF complex. The model calculations of the ν1(HF) band were performed assuming the band is a superposition of vibrational-rotational bands due to hot transitions from all low frequency hydrogen bond modes. © 1993.