Abstract Results of restricted Hartree-Fock(RHF) and density function theory(DFT) calculations are reported for 2-dicyanovinyl anthracene(2-DCVA) and 9-dicyanovinyl anthracene(9-DCVA) at B3LYP/6-311+G(d,p)//RHF/6-31G(d,p) level, the equilibrium geometries of 2-DCVA and 9-DCVA have been optimized and the harmonic vibrational frequencies have been calculated . The calculating results show that the ground state of 9- DCVA is higher than that of 2-DCVA in total energy; Having revolved angles between anthracene and dicyanovinyl from -180.0o to 180.0o,their potential energy curves are obtained to find their equilibrium geometries , The results show that there are two different stable geometries in energy and a transition geometry for 2-DCVA while there are a stable geometry and two transition geometries for 9-DCVA，the structure of 2-DCVA is more planar than 9-DCVA. At PM3/CIS level, their electronic spectrum were calculated and the vertical excitation energies and corresponding oscillator strengths from the ground states to the excited states are obtained. These results are in good agreement with the results obtained from experiment.
Key words 2-Dicyanovinyl anthracene, 9-Dicyanovinyl anthracene, Density function theory, Electronic spectrum

张敬来 苗体方 王 华 田安民#
(河南大学化学化工学院 河南开封 475001 ^#四川大学化学系 成都 610064)

摘要 用量子化学限制性自洽场和密度泛函方法，在B3LYP/6-311+G(d,p)//RHF/6-31G(d,p)水平上，对2-二氰基乙烯基蒽(2-DCVA)和9-二氰基乙烯基蒽(9-DCVA)分子进行了理论计算：优化得到了它们的平衡几何构型，并计算了它们的谐振动频率。结果表明：基态9-DCVA比基态2-DCVA的总能量高；在-180o～180o的范围内，旋转二氰基乙烯基和蒽基的夹角，计算了2-DCVA和9-DCVA的势能曲线，以寻找其可能存在的其它平衡几何构型，结果发现：2-DCVA有两个能量不同的稳定构型和一个过渡构型，而9-DCVA有一个稳定构型和两个过渡构型，2-DCVA的平面性比9-DCVA的好。在PM3/CIS水平上计算了它们的电子光谱，得到了由基态到各激发态的垂直跃迁能和相应的振子强度，计算结果与实验符合得很好。
关键词 2-二氰基乙烯基蒽 9-二氰基乙烯基蒽 密度泛函 电子光谱

张敬来 男，38岁，博士，现从事量子化学研究。
2002-05-10收稿，2002-07-07修回

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