The spectroscopic technique of threshold ion-pair production spectroscopy (TIPPS) has been applied to the triatomic molecule HCN. We have recorded the total ion-pair yield and TIPP spectra for the HCNH++CN process using coherent vacuum ultraviolet excitation. From the simulation of our high-resolution TIPP spectrum we have precisely measured the HCN ion-pair threshold EIP0 to be 122244±4cm1. This value could be used to determine the bond dissociation energy D0(HCN) to unprecedented accuracy. Our fitting result also showed that rotationally excited instead of cold CN fragment is favored as the ion-pair dissociation product in the threshold region.

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