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Knock in a Rotax-914 engine was modeled and investigated using an improved version of the KIVA-3V code with a G-equation combustion model, together with a reduced chemical kinetics model. The ERC-PRF mechanism with 47 species and 132 reactions [1] was adopted to model the end gas auto-ignition in front of the flame front. The model was validated by a Caterpillar SI engine and a Rotax-914 engine in different operating conditions. The simulation results agree well with available experimental results. A new engineering quantified knock criterion based on chemical mechanism was then proposed. Hydroperoxyl radical (HO2) shows obvious accumulation before auto-ignition and a sudden decrease after auto-ignition. These properties are considered to be a good capability for HO2 to investigate engine knock problems.