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首页> 外文期刊>Optical and Quantum Electronics >Static (hyper) polarizabilities and absorption spectra of single 2.2p-cyclophane NO2/NH2 substituted from DFT methods
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Static (hyper) polarizabilities and absorption spectra of single 2.2p-cyclophane NO2/NH2 substituted from DFT methods

机译：DFT方法取代的单个2.2p-环烷NO2/NH2的静态（超）极化率和吸收光谱

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摘要

We explore the behavior of the average of polarizability (), total first hyperpolarizability (beta(total)) and average of second hyperpolarizability () for single A/D (-NO2/-NH2) substituted 2.2p-cyclophane. The geometric optimization was carried out at HF and DFT (SVWN, PBE, B3LYP, PBE0, BHHLYP and CAM-B3LYP) level, in gas phase, using the 6-31 + G(d,p) basis set. The static tensor components of and beta(total), in gas phase, were calculated using Field Finite (FF) methods with electric field intensities of E = +/- 0.001 a.u. in each (x, y, z) axis direction. The substitution of A/D groups in positions 7-15 (structure 2 in Fig. 1) produced an increment in the values. Regardless of the A/D positions, the values showed not significant changes at all theory level. DFT results are overestimated up to 20, if HF values are taken into account, being SVWN and PBE functionals those that give the main deviation. There are monotonic and progressive behaviors of beta(total) for the 1-5 structure change as expected by orientation of the dipolar moment in both aromatic rings. With respect to the performance of DFT functionals, and beta(total) results are significantly overestimated if HF values are taken into account. In fact, the relative percentage error of beta(total) at DFT level with respect to HF ones is between 58 and 132, being PBE functional those that give the main deviation. The close overlap of the orbitals between the rings facilitates chromophore delocalization to account for the observation of high beta(total) in these compounds. Therefore, we expected that the contribution by coupling of the transition moment between first and higher excited states should be lie much higher due to phane effect than that for ring units.
机译：我们探讨了单个 A/D （-NO2/-NH2） 取代的 [2.2]p-环烷的极化率平均值 （）、总第一超极化率 （beta（total）） 和第二超极化率平均值 （） 的行为。采用6-31 + G（d，p）基集，在HF和DFT（SVWN、PBE、B3LYP、PBE0、BHHLYP和CAM-B3LYP）水平的气相中进行几何优化。采用场有限（FF）方法计算了气相中α>和β（总）的静态张值的增加。无论 A/D 位置如何，值在所有理论水平上均未显示显着变化。如果考虑 HF 值， DFT 结果被高估了 20%，因为 SVWN 和 PBE 泛函给出了主要偏差。对于1-5结构变化，β（总）存在单调和渐进行为，正如两个芳环中偶极矩的取向所预期的那样。关于DFT泛函的性能，如果考虑HF值，和β（总）结果被大大高估。事实上，在DFT水平上，beta（总）相对于HF的相对百分比误差在58%到132%之间，是PBE功能，给出了主要偏差。环之间轨道的紧密重叠有助于发色团离域，以解释在这些化合物中观察到高β（总）的原因。因此，我们预计第一激发态和高激发态之间的跃矩耦合贡献应该比环单元高得多。

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