物理化学学报 >> 2004, Vol. 20 >> Issue (12): 1428-1433.doi: 10.3866/PKU.WHXB20041206

研究论文 上一篇    下一篇

线性簇合物SC2nS2－(n =1～12)电子吸收光谱

张敬来;王连宾;吴文鹏;曹泽星   

  1. 河南大学化学化工学院,开封　475001;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
  • 收稿日期:2004-06-11 修回日期:2004-07-16 发布日期:2004-12-15
  • 通讯作者: 曹泽星 E-mail:zxcao@xmu.edu.cn

Electronic Absorption Spectra of Linear Cluster SC2nS2－(n=1～12)

Zhang Jing-Lai;Wang Lian-Bin;Wu Wen-Peng; Cao Ze-Xing   

  1. College of Chemistry and Chemical Engineering, Henan University, Kaifeng　475001;　 1State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen　361005
  • Received:2004-06-11 Revised:2004-07-16 Published:2004-12-15
  • Contact: Cao Ze-Xing E-mail:zxcao@xmu.edu.cn

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摘要： 应用密度泛函理论,在B3LYP/6-31G*水平上优化了线性簇合物SC2nS2－(n =1～12)的基态平衡几何结构,并计算了它们的谐振动频率.在基态平衡构型下,通过TD-B3LYP/cc-pvTZ和TD-B3LYP/cc-pvDZ计算,确定了簇合物SC2nS2－(n =1～10) 电子跃迁的垂直激发能和对应的振子强度.基于计算结果,导出了电子跃迁吸收波长与体系大小n的解析关系式,以及SC2nS2－体系第一电离能与体系大小n的解析表达式,并讨论了不同端位原子对碳链体系激发态性质的影响.

关键词: 线性簇合物SC2nS2－, 密度泛函理论（DFT）, 含时密度泛函理论（TD-DFT）, 电子光谱, 电离能, 解析表达式

Abstract: Using density functional theory(DFT),the geometries and the vibrational frequencies of linear cluster SC2nS2－(n=1～12) have been investigated at the B3LYP/6-31G* level. Time-dependent density functional theory(TD-DFT) has been used to calculate the vertical transition energies and oscillator strengths for transitions of SC2nS2－ at the B3LYP/cc-pvTZ and B3LYP/cc-pvDZ levels. On the basis of theoretical results, an explicit expression for the size dependence of the excitation energy in linear carbon chains is obtained. Present calculations show that the terminal sulfur atom may significantly affect the excited-state properties of the conjugated carbon chains. At the B3LYP/ 6-311＋G*level, the single-point energies of the ionic clusters have been calculated in order to determine the first ionization energies. The relationship between the cluster size and the first ionization energies of the linear carbon chains is proposed.

Key words: SC2nS2－, DFT, TD-DFT, Electronic spectra, Ionization energies, 　Analytic expression