【摘要】 为了研究叠氮化物的热解与光解机理发展了一些新式仪器,得到了一些与早期不同的实验结果。用量子化学从头计算方法(CASSCF,CI,MC CEPA,ACPF和CEPA)分析了实验结果和叠氮化银的光谱结构,描绘了叠氮化银光解的势能曲线,重新解释了其光解机理。沿着AgN -NN间的距离R2 所画的两个最低的三重态的势能曲线指示出,两个最低的单态势能曲线是叠氮化银的光解反应途径,在 2.18eV和 2.2 3eV处的两峰是基态分别向两个单态跃迁的结果更多还原

【Abstract】 Recently some new apparatus are developed to study thermal and photodecomposition mechanism of silver azide.The new experimental results are different from those reported previously. We have analysed the experimental results with abinitio calculations (CASSCF, valence CI, MC CEPA, ACPF and CEPA), assigned spectrum structure of AgN 3 ,plot the potential energy curves and reinterpreted the photodecomposition mechanism of the silver azide. The potential energy curves of two lowest singlet and two lowest triplet valence statesof AgN 3 along AgN-NN distance R 2 show that the two singlet valence states are involved in photodissociation of AgN 3 at two peaks of 2.18?eV and 2.23?eV respectively.更多还原