Ab initio electronic absorption spectra of para-nitroaniline in different solvents: Intramolecular charge transfer effects,Journal of Computational Chemistry

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Ab initio electronic absorption spectra of para-nitroaniline in different solvents: Intramolecular charge transfer effects
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-08-30 , DOI: 10.1002/jcc.27493
Matheus Máximo-Canadas ₁ , Lucas Modesto-Costa ₂ , Itamar Borges ₁

Affiliation

Intramolecular charge transfer (ICT) effects of para-nitroaniline (pNA) in eight solvents (cyclohexane, toluene, acetic acid, dichloroethane, acetone, acetonitrile, dimethylsulfoxide, and water) are investigated extensively. The second-order algebraic diagrammatic construction, ADC(2), ab initio wave function is employed with the COSMO implicit and discrete multiscale solvation methods. We found a decreasing amine group torsion angle with increased solvent polarity and a linear correlation between the polarity and ADC(2) transition energies. The first absorption band involves π → π* transitions with ICT from the amine and the benzene ring to the nitro group, increased by 4%–11% for different solvation models of water compared to the vacuum. A second band of pNA is characterized for the first time. This band is primarily a local excitation on the nitro group, including some ICT from the amine group to the benzene ring that decreases with the solvent polarity. For cyclohexane, the COSMO implicit solvent model shows the best agreement with the experiment, while the explicit model has the best agreement for water.

中文翻译：

对硝基苯胺在不同溶剂中的头头电子吸收光谱：分子内电荷转移效应

对硝基苯胺（pNA）在八种溶剂（环己烷、甲苯、乙酸、二氯乙烷、丙酮、乙腈、二甲基亚砜和水）中的分子内电荷转移（ICT）效应得到了广泛研究。二阶代数图结构 ADC（2），ab initio 波函数与 COSMO 隐式和离散多尺度溶剂化方法一起使用。我们发现胺基扭转角随着溶剂极性的增加而减小，极性与 ADC（2）转变能之间存在线性相关性。第一个吸收带涉及 ICT 从胺和苯环到硝基的 π → π* 转变，与真空相比，对于水的不同溶剂化模型，吸收带增加了 4%-11%。p NA 的第二个条带首次被表征。该谱带主要是硝基上的局部激发，包括从胺基到苯环的一些 ICT，这些 ICT 随溶剂极性的增加而减小。对于环己烷，COSMO 隐式溶剂模型与实验的一致性最佳，而显式模型对水的一致性最好。

更新日期：2024-08-30

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