Electronic structure of polystyrene: A valence effective Hamiltonian theoretical study
Electronic structure of polystyrene: A valence effective Hamiltonian theoretical study
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聚苯乙烯的电子结构：价态哈密顿理论研究
DOI：
10.1063/1.448226
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发表时间：
1985
影响因子：
4.4
通讯作者：
G. Street
中科院分区：
文献类型：
--
作者：
J. Brédas;G. Street
我们描述了侧基聚合物原型聚苯乙烯的能带结构和价态密度的价有效哈密顿量（VEH）计算。发现上面的两个占据带直接来自苯部分的上面的两个分子轨道，与杜克等人开发的分子离子模型一致。对于完全有规立构的链，计算出最高占据带的宽度为1 eV。考虑到固态效应，我们模拟了聚苯乙烯的理论UPS光谱，并将其与实验光谱进行了比较。只要适当考虑无序的影响，我们就能得到一个很好的整体雅阁，这使我们能够很容易地解释VEH能带结构的基础上的实验光谱中出现的峰的起源。这些结果表明，VEH技术可以可靠地应用于既有饱和和不饱和组分的聚合物。
We describe valence effective Hamiltonian (VEH) calculations of the band structure and density of valence states of polystyrene, the prototype of pendant‐group polymers. The upper two occupied bands are found to derive directly from the upper two molecular orbitals of the benzene moieties, in agreement with the molecular‐ion model developed by Duke et al. For a perfectly stereoregular chain, the highest occupied band is calculated to have a width of the order of 1 eV. Taking into account solid‐state effects, we simulate the theoretical UPS spectrum of polystyrene and compare it to the experimental spectrum. Provided the influence of disorder is properly considered, we obtain an excellent overall accord which permits us to easily interpret the origin of the peaks occurring in the experimental spectrum on the basis of the VEH band structure. These results indicate that the VEH technique can be applied reliably to polymers which have both saturated and unsaturated components.