Recent spectroscopic advances have led to the first determinations of infrared vibration‐rotation bands of polyatomic molecular ions. These initial detections were guided by abinitio predictions of the vibrational frequencies. The calculations reported here predict the vibrational frequencies of additional ions which are candidates for laboratory analysis. Vibrational frequencies of neutral molecules computed at three levels of theory, HF/3‐21G, HF/6‐31G*, and MP2/6‐31G*, were compared with experiment and the effect of scaling was investigated to determine how accurately vibrational frequencies could be predicted. For 92% of the frequencies examined, uniformly scaled HF/6‐31G* vibrational frequencies were within 100 cm1 of experiment with a mean absolute error of 49 cm1. This relatively simple theory thus seems suitable for predicting vibrational frequencies to guide laboratory spectroscopic searches for ions in the infrared. Hence, the frequencies of 30 molecular ions, many with astrochemical significance, were computed. They are CH+2, CH+3, CH+5, NH+2, NH+4, H3O+, H2F+, SiH+2, PH+4, H3S+, H2Cl+, C2H+, classical C2H+3, nonclassical C2H+3, nonclassical C2H+5, HCNH+, H2CNH+2, H3CNH+3, HCO+, HOC+, H2CO+, H2COH+, H3COH+2, H3CFH+, HN+2, HO+2, C3H+, HOCO+, HCS+, and HSiO+.

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