稠环芳烃菲电子激发态的含时密度泛函理论研究

用含时密度泛函理论TD-DFT及组态相关CIS、含时TD-HF方法对菲的UV光谱进行了理论研究，在几何构型优化的基础上，计算了其垂直电子激发能．计算表明，基函数的选择对激发能的计算影响较大，而不同的密度泛函交换一相关势对其影响较小，这和轨道能级的系统误差相互抵消有关．对菲的电子跃迁能的计算，与实验结果比较相一致，理论与实验的误差和不同的实验之间的误差在同一个数量级之内，显示TD-DFT方法比CIS，TD-HF方法更适合电子激发能的计算．

A Time-dependent DFT Study on the Electronic Excitation States of Polycyclic Aromatic Compound of Phenanthrene

The time-dependent DFT (TD-DFT), CIS and TD-HF studies have been performed on the UV-spectrum of phenanthrene. Based on the optimized geometries, the vertical excitation energies were calculated. The effect of basis sets is important on the excitation energies. Different exchange-correlation potentials hardly affected the excitation energies due to that the systematic errors of orbital energies were cancelled each other. The deviations between our theoretical results and experimental ones are in the same order of magnitude as that between different experimental methods. TD-DFT is more satisfactory than CIS and TD-HF on the electronic excitation energy calculations.