The XN XNCO (X = F, Cl, Br, I) PES experimental and quantum chemical study
|Course||Physical and chemical|
|Keywords||Ultraviolet photoelectron spectroscopy Ionization energy Gas - solid heterogeneous reaction Isomerization reaction Transition state|
The problem of air pollution is a hot issue in recent years, from all walks of life are very concerned about a series of small gaseous molecules NX (X = F, Cl, Br, Ⅰ) XNCO (X = F, Cl, Br, Ⅰ) electronic structure and related reactions, ultraviolet photoelectron spectrometer detected spectra, calculated nature of these several compounds combined quantum chemical calculations. Hope that these problems be helpful to clarify the performance and response of the atmospheric species. The method used herein to synthesis of small molecules in gaseous NX (X = Cl, Br) and XNCO (X = Cl, Br), is first proposed and used. The unique approach we first synthesized and detect the PES spectra of NX (X = Cl, Br), and on this basis, the use of in situ pyrolysis situ detection pyrolysis NX produce the NX and detect its spectra. Further gaseous the X Are 2 and AgOCN solid powder between the gas - solid heterogeneous reaction was successfully synthesized and detected XNCO (X = Cl, Br). In the experiment to detect more substances on the basis of HF, B3LYP method, MP2 method using STO-3G ,3-21G ,6-311 G (2df, pd) and SDB-aug-the cc-pVTZ basis respectively XN XNCO (X = F, Cl, Br, Ⅰ) series molecular configuration optimization, and calculate the frequency of vibration of the molecule, and by comparative analysis with the experimental data, the result of the calculation with B3LYP/SDB-aug-cc-pVTZ the most accurate. And the corresponding orbital symmetry calculation of molecular ionization, we use the HF method (using Koopmans theorem) OVGF (Outer Valence Green Functional) method as well as high-precision precision quantum chemical methods G2 method using 6-311 G (2DF, PD) basis set. Compared with experimental data analysis, the use of the G2 methods to get accurate first ionization energy, and OVGF methods are given in good agreement with the experimental results at all levels of ionizing energy, is the ideal method of calculating such calculations. Bidentate NCO group characteristics, we calculated theoretically the isomerization reaction the ClNCO ClOCN between the transition state, the activation energy from theory to predict the reaction. Quantum chemistry theory with experimental organic combination, to strive-depth study of gaseous small molecules NX (X = x Plant xN with xNco, Ha, Cx, sr, l, corpse Es experimental and quantum chemical study F, way, Br, I) and the nature of the XNCO (X = F, CI, Br, 1). Innovation in this article: z found a new method of synthesis of small gaseous molecules \\ X (X two CI, Br) and X \\ CO (X 2 Cl, Br). Used, into (X 2 CI, Br) heat the solution generating, solid powder occurs between the gas-solid heterogeneous reaction synthesis X, X, and with gaseous x (x = CI, Br) with AgOC CO are article first times proposed. Found suitable for on configuration of the molecular system optimization calculation method (B amp Ah basis set (SDB aug a - ee a PVTZ). 3, through the analysis and comparison of the calculated results to find the most suitable for such calculated the ionization energy of the molecule: the valence shell Green's function OVGF (outer Valence Green Funetional). 4, for the first time found CINCO AND CIOC, isomerization between the transition state of the reaction, and the reaction is calculated activation energy reveals that the reaction is an endothermic reaction.