Valence electronic structure of gas-phase 3,4,9,10-perylene tetracarboxylic acid dianhydride: Experiment and theory
Valence electronic structure of gas-phase 3,4,9,10-perylene tetracarboxylic acid dianhydride: Experiment and theory
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DOI：
10.1103/physrevb.73.195208
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发表时间：
2006-05-01
影响因子：
3.7
通讯作者：
Umbach, Eberhard
中科院分区：
文献类型：
--
作者：
Dori, Navit;Menon, Mahesh;Umbach, Eberhard
本文报道了3，4，9，10-二萘嵌苯四甲酸二酐（PTCDA）的气相紫外光电子能谱，并与凝聚相谱进行了比较。与对有机固体的普遍期望相反，我们观察到两者在许多细节上不同，需要重新审视我们对PTCDA电子结构的理论理解。因此，我们使用密度泛函理论与几个交换相关泛函，以及GW方法。我们发现局域密度近似和广义梯度近似不能描述实验数据，因为下界轨道集中在酸酐基团上。我们表明，这是校正的混合功能或GW方法，并使用结果来解释实验数据。
We present gas phase ultraviolet photoemission spectra of 3,4,9,10-perylene tetracarboxylic acid dianhydride (PTCDA) and compare them to condensed phase spectra. Contrary to common expectations for organic solids, we observe that the two differ in many details, necessitating a reexamination of our theoretical understanding of the PTCDA electronic structure. Thus, we use density functional theory with several exchange-correlation functionals, as well as the GW method. We find that the local density approximation and the generalized gradient approximation fail to describe the experimental data because of underbound orbitals that are concentrated on the anhydride groups. We show that this is corrected by either a hybrid functional or the GW method and use the results to interpret the experimental data.