论文标题

基于pariser-parr-pople模型的构型相互作用研究,对低对称性芳族烃分子中线性光吸收

Pariser-Parr-Pople Model based Configuration-Interaction Study of Linear Optical Absorption in Lower-Symmetry Polycyclic Aromatic Hydrocarbon Molecules

论文作者

Bhattacharyya, Pritam, Rai, Deepak Kumar, Shukla, Alok

论文摘要

具有较低对称性的各种多环芳烃(PAHS)的电子和光学特性,即苯并[Ghi] Perylyene(C $ _ {22} $ h $ _ {12} $),苯甲酸[A] coronene [a] coronene(c $ _ {28} $ h $ h $ _ $ _ $ _ $ _ $ _ {14} $ {14} $ [14} $ [14} $ [14} $ [14} $ [14} $] (c $ _ {32} $ h $ _ {16} $),anthra [2,3a] coronene(c $ _ {36} $ h $ _ {18} $)和naphtho [8,1,2-abc] coronene(c $ _ {30} $ h $ _ $ _ {14} $)为此,我们使用筛选的电子相关计算和$π$ - 电子Propar-pariser-parr-pople(PPP)Hamiltonian中的标准参数进行了,并且使用多互联态和激发态的相关效应包括多次朗读和激发态,多数referference duperiverles-dobles-double doubles doubles-doubl sopucturation-double nobles配置互动(MRSDCI)方法论。 PPP模型哈密顿量包括远程库仑相互作用,从而提高了我们计算的准确性。我们计算的结果预测,随着冠状衍生物的尺寸增加,光谱被红色移动,并且光学间隙减小。在每个频谱中,代表光学间隙的第一个峰具有中等强度,而更强烈的峰出现在较高的能量下。我们计算的光谱与可用的实验数据非常吻合。为了进行比较,我们还使用高斯基本函数对这些分子的光学间隙进行了第一原理的时间依赖性密度功能理论(TDDFT)计算,并发现它们产生的值低于我们的CI结果。

The electronic and optical properties of various polycyclic aromatic hydrocarbons (PAHs) with lower symmetry, namely, benzo[ghi]perylene (C$_{22}$H$_{12}$), benzo[a]coronene (C$_{28}$H$_{14}$), naphtho[2,3a]coronene (C$_{32}$H$_{16}$), anthra[2,3a]coronene (C$_{36}$H$_{18}$), and naphtho[8,1,2-abc]coronene (C$_{30}$H$_{14}$) were investigated. For the purpose, we performed electron-correlated calculations using screened, and standard parameters in the $π$-electron Pariser-Parr-Pople (PPP) Hamiltonian, and the correlation effects were included, both for ground and excited states, using the multi-reference singles-doubles configuration-interaction (MRSDCI) methodology. PPP model Hamiltonian includes long-range Coulomb interactions, which increase the accuracy of our calculations. The results of our calculations predict that, with the increasing sizes of the coronene derivatives, optical spectra are red shifted, and the optical gaps decrease. In each spectrum, the first peak representing the optical gap is of moderate intensity, while the more intense peaks appear at higher energies. Our computed spectra are in good agreement with the available experimental data. For the purpose of comparison, we also performed first-principles time-dependent density-functional theory (TDDFT) calculations of the optical gaps of these molecules using Gaussian basis functions, and found that they yielded values lower than our CI results.

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