细菌发光是是海洋中普遍存在的生物发光现象，对其研究已有半世纪之久，但是介于多步反应过程的复杂性，现对细菌生物发光的机理仍然是一知半解。本工作主要对细菌发光反应中的加氧过程进行研究，从理论上分析自由基对形成-复合机理的合理性。计算中以AUG-cc-PVDZ为基组，采用密度泛函理论DFT中的M06-2X泛函方法，分析细菌发光加氧反应中涉及的分子的几何构型、振动频率、电子抽取能、势能曲线及反应能量等信息。结果显示：（1）加氧反应是按照自由基对形成-复合机理进行，即氧分子与荧光素阴离子经但电子转移过程，形成超氧负离子和荧光素自由基对，后自由基对复合得到过氧化物中间体；（2）与甲苯和水溶剂相比，气相环境最有利于反应的进行。

Bacterial bioluminescence (BL) is ubiquitous in the ocean and has attracted the attention of researchers for half a century.But the mechanism of bacterial BL is still largely unknown due to the complexity of the multistep reaction process.This work is mainly on the O2 addition process in bacterial BL,in order to explain the mechanism of a radical pair formation and recombination from the perspective of theory. In the computation,geometry optimization calculations were made at the M06-2X/AUG-cc-PVDZ level of theory,as well as frequency,electron extraction potentials,potential energy curve and reaction energies calculations.This investigation revealed that (1) the O2 addition process is carried out in accordance with the mechanism of a radical pair formation and recombination,that is to say the formation of peroxide intermediate involves a intermolecular one-electron transfer to form a radical pair of neutral luciferin radical and superoxide,followed by a radical recombination.(2)Compared with toluene and water solvent,gas phase is the most conductive environment for such reactions.