Wang Xia, Liu Zeyu, Yan Xiufen, Lu Tian, Wang Haowei, Xiong Weiwei, Zhao Mengdi
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. 2022 Mar 23;24(12):7466-7473. doi: 10.1039/d1cp05883e.
The electronic spectra and (hyper)polarizability of C-(CO) ( = 2, 4, and 6) are studied using theoretical calculations to reveal the effect of introducing carbonyl (-CO) groups on the molecular optical properties. Successive introduction of -CO groups is observed to cause a red-shift in the absorption spectrum, but maximum absorption of all molecules is mainly due to the charge redistribution within the C moiety. The (hyper)polarizabilities of the cyclocarbon oxides present an ascending trend with the -CO groups in the molecule, and the higher-order response properties are more sensitive. With (hyper)polarizability density analysis and (hyper)polarizability contribution decomposition, the fundamental reasons for the difference of (hyper)polarizability of different molecules are systematically discussed from the perspective of physical and structural origins, respectively. Significant optical resonances under the frequency-dependent fields are found for the (hyper)polarizabilities of the cyclocarbon oxides, which is in contrast to the insignificant influence on their polarizability.
利用理论计算研究了C-(CO)（= 2、4和6）的电子光谱和（超）极化率，以揭示引入羰基（-CO）基团对分子光学性质的影响。观察到连续引入-CO基团会导致吸收光谱发生红移，但所有分子的最大吸收主要归因于C部分内的电荷重新分布。环碳氧化物的（超）极化率随分子中-CO基团的增加呈上升趋势，且高阶响应特性更为敏感。通过（超）极化率密度分析和（超）极化率贡献分解，分别从物理和结构起源的角度系统地讨论了不同分子（超）极化率差异的根本原因。发现环碳氧化物的（超）极化率在频率相关场下存在显著的光学共振，这与其极化率受影响不显著形成对比。
