Photoelectron spectroscopy of terpenoids and prediction of their rate constants in atmospheric oxidation reactions  

作　　者：WANG XiaoPeng TONG ShengRui GE MaoFa WANG WeiGang WANG DianXun 

机构地区：[1]Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species,Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

出　　处：《Chinese Science Bulletin》2010年第35期4018-4025,共8页

基　　金：supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (KJCX2-YW-N24,KZCX2-YW-Q02-03);the National Basic Research Program of China (2006CB403701);the National Natural Science Foundation of China (40925016,40830101)

摘　　要：The electronic structures of six mono-terpenoids and two of their oxygenated derivatives were studied by He I photoelectron spectroscopy(PES).The observed bands were interpreted on the basis of empirical arguments and theoretical calculations.The first vertical ionization potentials for β-pinene,α-terpinene,terpinolene,γ-terpinene,limonene,myrcene,citral,and terpinene-4-ol were determined to be 8.73,7.57,8.26,8.30,8.53,8.68,8.71,and 8.77 eV,respectively.Most of these values have not been determined by PES before.The correlations of the first vertical ionization potentials of these compounds to the natural logarithms of rate constants for their reactions with the radicals OH,NO3,and O3 were determined.The correlation coefficients for their reactions with OH,NO3,and O3 were 0.97,0.91,and 0.95,respectively.This method is a powerful technique for predicting the rate constants for the atmospheric oxidation reactions of terpenoids.The electronic structures of six mono-terpenoids and two of their oxygenated derivatives were studied by He I photoelectron spectroscopy （PES）. The observed bands were interpreted on the basis of empirical arguments and theoretical calculations. The first vertical ionization potentials for ,8-pinene, ct-terpinene, terpinolene, y-terpinene, limonene, myrcene, citral, and ter- pinene-4-ol were determined to be 8.73, 7.57, 8.26, 8.30, 8.53, 8.68, 8.71, and 8.77 eV, respectively. Most of these values have not been determined by PES before. The correlations of the first vertical ionization potentials of these compounds to the natural logarithms of rate constants for their reactions with the radicals OH, NO3, and 03 were determined. The correlation coefficients for their reactions with OH, NO3, and O3 were 0.97, 0.91, and 0.95, respectively. This method is a powerful technique for pre- dicting the rate constants for the atmospheric oxidation reactions of terpenoids.

关 键 词：反应速率常数 萜类化合物 光电子能谱 氧化反应 大气 垂直电离势 预测 异松油烯 

分 类 号：O643.11[理学—物理化学] O629.61[理学—化学]