Theoretical studies of electronic properties of polyacene, poly(1,4-dihydrobenzo-1,4-dihydrobenzene), poly(p-phenylene), poly(p-1,4-dihydrobenzene), and their hetero (N, O, and S) substituted derivatives
Theoretical studies of electronic properties of polyacene, poly(1,4-dihydrobenzo-1,4-dihydrobenzene), poly(p-phenylene), poly(p-1,4-dihydrobenzene), and their hetero (N, O, and S) substituted derivatives
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多并苯、聚(1,4-二氢苯并-1,4-二氢苯)、聚(对亚苯基)、聚(对1,4-二氢苯)及其杂原子(N、O和
DOI：
10.1021/ja00248a004
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发表时间：
1987
影响因子：
15
通讯作者：
A. Lilly
中科院分区：
文献类型：
--
作者：
J. Kao;A. Lilly
本文采用基于分子轨道的分子力学方法（MOMM）对苯、吡啶、吡嗪、1，4-二氢苯、1，4-二氢吡嗪、1，4-二恶英和1，4-二噻英的结构进行了推导。用同样的方法计算了上述化合物的低聚体结构，导出了多并苯、多聚（吡啶并吡啶），聚聚吡嗪并吡嗪（1，4-二氢苯并-1，4-二氢苯），聚（1，4-二氢吡嗪并-1，4-二氢吡嗪），聚（1，4-二氧杂环己-1，4-二氧杂环己烯）和聚（1，4-二噻英并-1，4-二噻英）、聚（对亚苯基）、聚（对吡嗪）、聚（1，4-二氢苯）、聚（对-1，4-二氢吡嗪）、聚（对-二恶英）和聚（对二噻英）。这些聚合物的能带结构，态密度，电离势，带隙，还原电位和氧化电位，然后通过使用价有效哈密顿方法（VEH）计算。聚（p-吡嗪）被预测为具有与聚（p-亚苯基）大致相同的导电特性，前者通过受体的p-掺杂性略差，而通过供体的n-掺杂性略高。与以前报道的值和解释相反，我们的结果更符合聚（pyridinopyridine）和聚（pyrazinopyrazine）的实验数据。目前VEH参数化的陷阱进行了讨论。已发现氦原子对这些聚合物进行了可观的改性。硫取代的聚合物被发现是特别有趣的导电聚合物。讨论了结构对电子性质的影响，理论计算已被广泛应用于解释和组织结果以及解决化学奥秘。理论计算在未来可能发挥的最重要作用，可能是在任何昂贵的实验工作开始之前作出正确的预测。不幸的是，目前没有一种方法，是足够的所有问题的计算精度和所需的计算机时间。因此，应鼓励进行系统的研究。这种研究对于有用的预测可能是必要的，因为它们增加了“消除误差”的有效性，并进行了系统的校正
A molecular-orbital-based molecular mechanics method (MOMM) has been employed to derive the structures of benzene, pyridine, pyrazine, 1, 4-dihydrobenzene, 1, 4-dihydropyrazine, 1, 4-dioxin, and 1, 4-dithiin. The oligomerstructures of the above compounds have also been calculated by using the same method to derive the unit cells of polyacene, poly (pyridinopyridine), poly (pyrazinopyrazine), poly (l, 4-dihydrobenzo-l, 4-dihydrobenzene), poly (1, 4-dihydropyrazino-1, 4-dihydropyrazine), poly (1, 4-dioxino-1, 4-dioxin), and poly (1, 4-dithiino-1, 4-dithiin), poly (p-phenylene), poly (p-pyrazine), poly (pl, 4-dihydrobenzene), poly (p-1, 4-dihydropyrazine), poly (/?-dioxin), and poly (p-dithiin). The band structures, densities of states, ionization potentials, bandgaps, reduction potentials, and oxidation potentials of these polymers have then been calculated by using the Valence Effective Hamiltonian method (VEH). Poly (p-pyrazine) is predicted to have about the same conduction characteristics as poly (p-phenylene), the former being slightly less p-dopable by acceptors while being slightly more n-dopable by donors. In contrast to previously reported values and interpretation, our results are more in line with experimental data for poly (pyridinopyridine) and poly (pyrazinopyrazine). Pitfalls of the current VEH parametrization are discussed. Hetero atoms have been found to makeconsiderable modifications for these polymers. Sulfur-substituted polymers are found to be particularly interesting in terms of conductingpolymers. The structural effects on electronic properties are discussed.Theoretical calculations have been widely applied to interpret and organize results and to resolve chemical mysteries. The most important role theoretical calculations may play forthe future is probably to make correct predictions before any costly exper-imental work begins. Unfortunately, there is currently no single method that is adequate for all problems in terms of both the calculated accuracy and the required computer time. Thus, systematic studies should be encouraged. Such studies may be necessary for useful predictions because they increase the effec-tiveness of “cancellation of errors” and make systematic corrections