戊烯自由基阳离子的密度泛函理论研究  

DFT Study of the Pentene Radical Cations:Molecular and Hyperfine Structures

作　　者：赵彦英[1] 刘亚军[1] 郑世钧[1] 黄明宝[2] 孟令鹏[1] 

机构地区：[1]河北师范大学计算量化研究室,石家庄050091 [2]中国科学院研究生院化学部,北京100039

出　　处：《物理化学学报》2002年第12期1081-1086,共6页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20173056)~;河北省自然科学基金(201098)资助项目~

摘　　要：使用密度泛函理论B3LYP方法和6-31G(d,p)、6-31+G(d,p)、6-311G(d,p)及6-311+G(d,p)基组,分别对2-C5H10+和1-C5H10+的各种构象进行了几何构型优化,并用B3LYP/6-311G(d,p)进行了频率分析计算.计算预言1-C5H10+具有非平面构型,与以往报导的从头算计算结论相反.在两个自由基阳离子的各种构象的B3LYP几何构型上,进行了B3LYP和UMP2(full)方法的超精细偶合常数计算,得到了比以往更好的结果.The density function theory (DFT) B3LYP study on the 2-C5H10+ and 1-C5H10+ radical cations has been carried out. The molecular geometries for various conformations of the two cations were optimized at the B3LYP/6-31G(d,p), B3LYP/6-31 + G(d, p), B3LYP/6-311G(d, p), and B3LYP/6-311 + G(d, p) levels, and the frequency analysis calculations were performed at the B3LYP/6-311G(d, p) level. The 1-C5H10+ ion was predicted to have a nonplanar structure, which is in contrast to the previous conclusions based on ab initio calculations. Based on the B3LYP/6-311G(d, p) geometries, the proton isotropic hyperfine coupling constants (HFCCs) were calculated at the B3LYP/6-311G(d, p) and MP2 (full)/6-311G(d, p) levels. The calculated HFCCs results are in good agreement with experiment and more accurate than the previous theoretical results.

关 键 词：戊烯自由基阳离子 密度泛函理论 超精细结构 B3LYP 

分 类 号：O643.1[理学—物理化学]