反式亚硝酸与顺式亚硝酸异构化反应机理的理论研究

用量子化学从头算方法,在ＭＰ２／６－３１Ｇ水平上对反式亚硝酸面外异构化为顺式亚硝酸反应的机理进行了研究． 计算表明：该反应为放热反应,活化势垒为５３．４１ ｋＪ·ｍ ｏｌ－ １．     

HONO与HCl反应的量子化学研究

用量子化学密度泛函理论(DFT)和四次组态相互作用(QCISD(T)),对HONO与HCl的反应进行了研究.在B3LYP/6-311G**计算水平上,优化了反应势能面上各驻点的几何结构.在QCISD(T)/6-311G**水平上计算了单点能量.确定了反应机理,HONO与HCl反应主要生成产物为ClNO H2O.     

A novel heterogeneous reaction for generating gaseous nitrous acid

The short-lived reactive specimen nitrous acid HONO was generated in the gas phase by the hetero-geneous reaction of gaseous HCl with AgNO2 which can generate higher concentration of HONO than other methods. We investigated the process from generation to dissociation in the gas phase under different controlled temperatures,and discussed the ionization and reaction on the solid surface by combination of the photoelectron spectroscopy and photoionization mass spectroscopy(PES-PIMS) and in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) .     

A novel heteroseneous reaction for generating gaseous nitrous acid

The short-lived reactive specimen nitrous acid HONO was generated in the gas phase by the heterogeneous reaction of gaseous HCl with AgNO2 which can generate higher concentration of HONO than other methods. We investigated the process from generation to dissociation in the gas phase under different controlled temperatures, and discussed the ionization and reaction on the solid surface by combination of the photoelectron spectroscopy and photoionization mass spectroscopy （PES-PIMS） and in situ diffuse reflectance infrared Fourier transform spectroscopy （DRIFTS）.     

新型在线光谱测量方法在环境排放中的应用

 新型在线光谱测量方法, 如宽带腔增强吸收光谱及可调谐半导体激光吸收光谱技术, 由于其高灵敏度、原位实时以及较好的时间空间分辨率, 被广泛应用于环境排放监测。本文结合实际测量案例, 对腔增强吸收光谱技术在气态亚硝酸、气溶胶消光及可调谐激光在选择性催化还原脱硝中的液膜多参数测量中的应用研究做了总结回顾, 并认为两种测量技术的发展结合, 将为大气化学反应的核心活性物种测量、气溶胶消光参数的准确定量及非均相大气反应动力学测量提供有效的方法。     

1,3,3-三硝基氮杂环丁烷的HONO消去反应机理的理论研究

用密度泛函理论B3LYP/6-31 G(d, p)方法对1,3,3-三硝基氮杂环丁烷(TNAZ)的五中心消去反应机理进行了理论研究. 计算发现了两个不同的HONO消去反应途径,得到了这两个反应途径中反应物、过渡态和中间产物的平衡构型、谐振频率、能量及零点能. 计算结果表明两个HONO消去热分解途径可以相互竞争,并预测该途径是固体TNAZ热分解的重要途径之一.