气相硝酸及过氧亚硝酸的结构和光电子能谱

采用了B3LYP方法和6-311G(d) 基组，并辅以MP2方法详细地计算了硝酸(HONO2)和过氧亚硝酸(HOONO)及相应正离子的各种可能构象、能量、振动频率等，分析了它们的相对稳定性、电离势、光电子能谱，探讨了用光电子能谱去探测HOONO的可能性.结构优化结果表明， HOONO和HOONO＋均有三种稳定的构象， HOONO有三个一阶鞍点的结构.作出了HOONO和HOONO＋的能量随O－O键旋转的变化曲线图，定性地讨论了可能存在的物种以及各构象之间几何结构的变化.

Structure and Photo Electron Spectroscopy of HONO2 and HOONO

The equilibrium structures, frequencies and energies of HONO2 , , HOONO conformers and HOONO+conformers are calculated in detail by density function theory(DFT) at B3LYP theory level with 6 311G(d) basis set. The calculated results indicate that HOONO and HOONO+ both have three stable conformers, and HOONO has three structures with imaginary frequencies. Additionally, the potential energy curves of rotation of O-O bond of HOONO and HOONO+ are calculated and used to discuss the geometry change between different conformers. The active vibrational modes in the photo electron spectra(PES) of HONO2 and HOONO conformers are predicted based on our calculated equilibrium structures and vibrational frequencies.