重氮苯与亲核试剂的作用方式及其反应机理一直未能被完全阐明.基于密度泛函理论,本文计算了6种亲核试剂与重氮苯结合时的结合位点及反应过程中的反应坐标.计算结果表明,化学硬度可以作为预测不同亲核试剂与重氮苯结合位点的主要描述符.基于复合物体系范德华表面的平均局域离子化能等参数,还提出了可以定量预测重氮苯与亲核试剂结合反应活化能垒的描述符.这些理论研究结果对理解重氮苯与亲核试剂的反应机制、寻找更优反应条件具有重要意义.“,”The specific interaction and reaction mechanism between aromatic diazonium salts and nucleophi-lic reagents have not been fully clarified yet. Within the framework of density functional theory,we calculated the binding sites and reaction coordinates of six different nucleophiles with diazobenzene. Chemical hardness of the attacking atom is the main descriptor for describing the binding site. Moreover,a quantitative descriptor is proposed to predict the activation energy barrier in terms of local ionization energy and charge distribution . These results are useful to gain insight for understanding the reaction mechanism of reactions involving aroma-tic diazonium salts and to explore better reaction conditions.