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With the aim of elucidating the mechanism causing abnormal combustion, a study was made of light emission and absorption characteristics at wavelengths corresponding to the spectra of the OH (characteristic spectrum of 306.4 nm), CH (431.5 nm), C2 (516.5 nm) radicals. Spectral properties were measured in the end-gas region of the cylinder for various types of fuel having different octane numbers. During combustion in an actual engine, the behavior of the CH and C2 radicals prior to the occurrence of abnormal combustion characterized by knock is indicative of behavior in the negative temperature coefficient (NTC) region. The experimental results revealed that the behavior of the OH, CH, C2 radicals differs between normal and abnormal combustion.