新Cu(II)配合物在选定密度泛函中结构-性质关系的比较评估。

Davut Avcı, Hatice Esra Cömert, Fatih Sönmez, Necmi Dege, Ömer Tamer, Yusuf Atalay
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引用次数: 0

摘要

为了用DFT方法评价Cu(II)配合物的结构-性能关系,用XRD、FTIR、UV-Vis和荧光光谱方法研究了新合成的Cu(Ⅱ)配合物[Cu(6-Brpic)2(bpy)]的结构。此外,还进行了Hirshfeld表面和NBO分析,以确定分子间和配位环境中可能的相互作用。考虑几何参数(键长和角度)、振动频率、电子吸收波长、,电子跃迁以及线性和非线性光学参数。结构和振动参数的R2,以及MPD%、MAD、最佳比例因子(λ)和总均方根(RMS)偏差,仅在振动频率下考虑。虽然已经确定M06-L和TPSSTPSS能级对于Cu(II)络合物的键长和角度给出了最佳结果,但是对于振动频率的最佳结果是在HCTH方法以及这些方法中获得的。在NLO参数中,静态和动态一阶超极化率(和β(-ω;ω,0)/)值,在HCTH方法中获得最大值(38.817×10-30和437.86×10-30/201.55×10-30esu),而在CAM-B3LYP/TPSTPSS水平中发现最小值(6.118×10-30ESu,8.270×10-30/11.730×10-30es u)。关于静态γ()和动态(参数),M06L(232.101×10-36)和HCTH(1711.52×10-36。事实上,可以明显看出,通过上述DFT水平获得的β和γ值比尿素的标准分子高出许多倍。这些结果表明,Cu(II)配合物可以作为一种潜在的NLO材料来发展光电子器件。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Comparative assessment of structure-property relationships of new Cu(II) complex in selected density functionals.

In order to evaluate the structure-property relationships of Cu(II) complex by using DFT methods, the structure of the newly synthesized Cu(II) complex, [Cu(6-Brpic)2(bpy)], was investigated by XRD, FTIR, UV-Vis, and fluorescence spectroscopic methods. In addition, Hirshfeld surface and NBO analyses were fulfilled to identify possible interactions in the intermolecular and coordination environment. The five different DFT methods (HCTH, M06L, TPSSTPSS, B3LYP, and CAM-B3LYP levels), having four different functionalities (the GGA, meta-GGA, hybrid-GGA, and range-separated hybrid), were carried out so as to investigate the structure-property relationship, considering the geometric parameters (bond lengths and angles), vibrational frequencies, electronic absorption wavelengths, electronic transitions, and linear and nonlinear optical parameters. The R2 for structural and vibrational parameters, as well as MPD%, MAD, an optimal scaling factor (λ) and overall root mean square (RMS) deviation, were considered only at vibration frequencies. While it was determined that M06-L and TPSSTPSS levels gave the best results for the bond lengths and angles of the Cu(II) complex, the best results for vibrational frequencies were obtained in the HCTH method along with these methods. In NLO parameters, the static and dynamic first-order hyperpolarizability (<β(0;0,0)> and β(-ω;ω,0)/<β(-2ω;ω,ω)>) values, the largest values were obtained in the HCTH method (38.817 × 10-30 and 437.86 × 10-30/201.55 × 10-30 esu), whereas the smallest values were found to be in the CAM-B3LYP/TPSSTPSS levels (6.118 × 10-30 esu, 8.270 × 10-30/11.730 × 10-30 esu). By regarding the static γ (<γ(0;0,0,0)>) and dynamic (<γ(-ω;ω,0,0)> parameters, the largest values were calculated in the M06L (232.101 × 10-36) and HCTH (1711.52 × 10-36) methods and the smallest values were obtained in the CAM-B3LYP (43.281 × 10-36 and 60.844 × 10-36) method. In fact, it is obviously seen that the β and γ values obtained by the aforementioned DFT levels are many times higher than that of the standard molecule of urea. These results indicate that the Cu(II) complex may be used as a potential NLO material to evolve optoelectronic devices.

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