On the contribution of f electrons to the quadratic hyperpolarizability: the case of lanthanide terpyridyl complexes†,Physical Chemistry Chemical Physics

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On the contribution of f electrons to the quadratic hyperpolarizability: the case of lanthanide terpyridyl complexes†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-02-27 00:00:00 , DOI: 10.1039/c8cp00853a
Fatima Ibersiene _{1,

2,

3,

4,

5} , Camille Latouche _{6,

7,

8,

9,

10} , Claudine Katan _{10,

11,

12,

13,

14} , Abdou Boucekkine _{10,

11,

12,

13,

14}

Affiliation

Over the last decades, trivalent lanthanide ions (Ln³⁺) have gained much attention due to their peculiar luminescence, which opened the way to a broad range of applications, from medical diagnostic to lasers. Their impact on nonlinear optical (NLO) properties also attracted interest, especially in the framework of lanthanide complexes. Several experimental studies demonstrated that the quadratic hyperpolarizability varies with the number of 4f-electrons, with a stronger effect on dipolar than octupolar components. The main interpretation put forward to explain the observed trends relied on the polarizable character of the 4f-electrons. We report here a first step towards understanding the role of 4f-electrons in NLO responses, considering a series of dipolar terpyridyl-trinitro lanthanide complexes LLn(NO₃)₃ (Ln = Gd, Dy, Yb, Lu as well as La and Y; L = terpyridil-like ligand). Using DFT and TD-DFT we investigate their linear and non-linear optical properties. Consistently with earlier experimental findings, simulated UV-visible spectra show minor changes by varying Ln. The same holds for dipole moments and polarizabilities, whereas the nature of the lanthanide affects hyperpolarizabilities. It is shown that the observed changes are not a direct effect of the 4f-electrons that behave like core electrons.

中文翻译：

关于f电子对二次超极化性的贡献：镧系元素吡啶基吡啶配合物†

在过去的几十年中，三价镧系离子（Ln ³⁺）由于其独特的发光特性而备受关注，这为从医学诊断到激光的广泛应用打开了道路。它们对非线性光学（NLO）性质的影响也引起了人们的兴趣，特别是在镧系元素络合物的框架中。几项实验研究表明，二次超极化率随4f电子数量的变化而变化，对偶极子的影响要比八极子的强。提出主要解释是根据4f电子的可极化特性来解释观察到的趋势。考虑到一系列偶极三联吡啶基-三硝基镧系元素络合物，我们在这里报告了迈向了解4f电子在NLO反应中的作用的第一步L Ln（NO ₃）₃（Ln = Gd，Dy，Yb，Lu以及La和Y；L =像哌替啶的配体）。使用DFT和TD-DFT，我们研究了它们的线性和非线性光学特性。与早期的实验结果一致，模拟的紫外-可见光谱显示出通过改变Ln的微小变化。偶极矩和极化率也是如此，而镧系元素的性质会影响超极化率。结果表明，观察到的变化不是表现为核心电子的4f电子的直接影响。

更新日期：2018-02-27

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