聚炔烃电子吸收光谱的理论研究  

Electronic Spectra of Polyynes HC_(2n)H

作　　者：张聪杰[1,2] 曹泽星[1] 武海顺[2] 徐昕[1] 张乾二[1] 

机构地区：[1]厦门大学化学系,固体表面物理化学国家重点实验室 [2]山西师范大学化学系,临汾041004

出　　处：《物理化学学报》2002年第7期585-589,共5页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20173042)资助项目

摘　　要：应用DFT/B3LYP方法,在6-31G水平上计算了HC2nH(n=1～13)的基态平衡几何构型和振动频率.在基态平衡构型下,通过TD-B3LYP/cc-PVTZ计算,确定了HC2nH(n=1～5)体系X1Σ+g11Σ+u电子跃迁的能量和对应的振子强度.根据计算结果并结合先前的价键研究导出了HC2nH聚炔烃体系X1Σ+g11Σ+u电子跃迁能与体系大小n有关的解析表达式.Density functional theory with the B3LYP functional is used to determine the geometries and vibrational frequencies of HC 2nH (n=1～13). The vertical transition energies of HC 2nH (n=1～5) havebeen estimated by TD B3LYP/cc PVTZ calculations.On the basis of theoretical calculations,a generally analytic expression for the chain size n dependence of the vertical transition energy was suggested,which can predict excellent excitation energies in comparison with available observed bands.Current calculations reveal that a nonlinear behavior for the even numbered HC2nH between the excitation energy and the number of carbon atoms.

关 键 词：电子吸收光谱 聚炔烃 TD-B3LYP 解析表达式 密度泛函 电子跃近 振动频率 激发能 

分 类 号：O657.3[理学—分析化学]