摘要
选用7种不同的密度泛函理论方法,在全电子双ζ加极化加弥散函数基组(DZP++)下,对烷基硫自由基及其负离子进行系统研究,获得它们的基态结构和电子亲合能.结果表明,B3LYP方法预测的绝热电子亲合能与实验值吻合,平均绝对误差是0.047 eV;预测的电子亲合能分别为1.838 eV(CH3S),1.925 eV(C2H5S),1.939 eV(n-C3H7S),1.961 eV(n-C4H9S),1.969 eV(n-C5H11S),2.023 eV(i-C3H7S)和2.055 eV(t-C4H9S).
Seven different density functional theory methods have been employed to predict the molecular structures and adiabatic electronic affinities of RS/RS (R=CH3, C2H5, n-C3H7, n- C4H9, n-C5 H11, i-C3H7, t-C4H9 ) radicals and their anions. The basis used is of double-ξ plus polarization quality with additional s-and p-type diffuse functions, labeled as DZP++. The most reliable adiabatic electron affinities, obtained by B3LYP methods, are 1. 838 eV (CH3S), 1. 925 eV(C2H5S), 1. 939 eV(n-C3H7S), 1. 961 eV(n-C4H9S), 1. 969 eV(n-C5H11S), 2. 023 eV(i- C3H7S), and 2. 055 eV(t-C4H9S), respectively. Compared with the experimental values, the average absolute error of the B3LYP method remained only 0. 047 eV.
出处
《北京理工大学学报》
EI
CAS
CSCD
北大核心
2010年第3期340-347,共8页
Transactions of Beijing Institute of Technology
基金
国家自然科学基金资助项目(20773014)
关键词
烷基硫自由基
分子结构
密度泛函理论
电子亲合能
alkylthion radicals
molecular structures
density functional theory
electron affinities