Liu Zeyu, Wang Jiaojiao, Zhou Qing, Lu Tian, Wang Xia, Yan Xiufen, Zhao Mengdi, Yuan Aihua
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, People's Republic of China.
Beijing Kein Research Center for Natural Sciences, Beijing 100022, People's Republic of China.
Phys Chem Chem Phys. 2023 Nov 1;25(42):29165-29172. doi: 10.1039/d3cp04150f.
Based on a computational approach that can accurately describe their geometric structures and electronic spectra, we have theoretically studied the nonlinear optical (NLO) properties of H-capped carbon chains, H-(CC)-H ( = 3-15), for the first time. Special attention was paid to the size dependence of the molecular (hyper)polarizability of these species through the nonlinear fitting of the data, which formed two power-law formulas of (∞) = -0.206 + 0.264 and (∞) = -0.624 + 0.006 and was thoroughly discussed at the electronic structure level by in-depth wavefunction analyses. The fundamental gap (Δ) between vertical ionization energy (VIE) and vertical electron affinity (VEA) is found to be related to the molecular (hyper)polarizability. The calculated (hyper)polarizability of the carbon chais H-(CC)-H ( = 3-15) is more sensitive to the density functional theory (DFT) applied than to the basis set selected. The results are expected to provide theoretical guidance for the property prediction of arbitrarily long carbon chains not yet synthesized.
基于一种能够精确描述其几何结构和电子光谱的计算方法，我们首次从理论上研究了氢封端碳链H-(CC)-H（= 3 - 15）的非线性光学（NLO）性质。通过对数据进行非线性拟合，特别关注了这些分子的（超）极化率的尺寸依赖性，拟合得到了两个幂律公式(∞) = -0.206 + 0.264和(∞) = -0.624 + 0.006，并通过深入的波函数分析在电子结构层面进行了充分讨论。发现垂直电离能（VIE）和垂直电子亲和能（VEA）之间的基本能隙（Δ）与分子的（超）极化率有关。碳链H-(CC)-H（= 3 - 15）的计算（超）极化率对所应用的密度泛函理论（DFT）比对所选基组更为敏感。预期这些结果将为尚未合成的任意长碳链的性质预测提供理论指导。
