物理化学学报 >> 2002, Vol. 18 >> Issue (07): 585-589.doi: 10.3866/PKU.WHXB20020703

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聚炔烃电子吸收光谱的理论研究

张聪杰;曹泽星;武海顺;徐昕;张乾二   

  1. 厦门大学化学系,固体表面物理化学国家重点实验室,厦门　361005;山西师范大学化学系,临汾　041004
  • 收稿日期:2001-11-14 修回日期:2001-12-28 发布日期:2002-07-15
  • 通讯作者: 曹泽星 E-mail:zxcao@xmu.edu.cn

Electronic Spectra of Polyynes HC 2nH

Zhang Cong-Jie;Cao Ze-Xing;Wu Hai-Shun;Xu Xin;Zhang Qian-Er   

  1. Department of Chemistry,State Key Laboratory for Physical Chemistry of the Solid Surface,Xiamen University,Xiamen　361005;Department of Chemistry,Shanxi Normal University,Linfen　041004
  • Received:2001-11-14 Revised:2001-12-28 Published:2002-07-15
  • Contact: Cao Ze-Xing E-mail:zxcao@xmu.edu.cn

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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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电子跃迁能与体系大小n有关的解析表达式.

关键词: 聚炔烃, TD-B3LYP, 电子光谱, 解析表达式

Abstract: 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) have been 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.

Key words: Polyynes, TD-B3LYP, Electronic spectra, Analytic expression