Cui Yanling, Li Yafei, Dai Yumei, Verpoort Francis, Song Peng, Xia Lixin
College of Physics and Chemistry, Liaoning University, Shenyang 110036, PR China.
Normal College, Shenyang University, Shenyang 110044, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2016 Feb 5;154:130-134. doi: 10.1016/j.saa.2015.10.038. Epub 2015 Oct 24.
In the present work, TDDFT has been used to investigate the excited state intramolecular proton transfer (ESIPT) mechanism of a new chromophore II [Sensors and Actuators B: Chemical. 202 (2014) 1190]. The calculated absorption and fluorescence spectra agree well with experimental results. In addition, two types of II configurations are found in the first excited state (S1), which can be ascribed to the ESIPT reaction. Based on analysis of the calculated infrared (IR) spectra of O-H stretching vibration as well as the hydrogen bonding energies, the strengthening of the hydrogen bond in the S1 state has been confirmed. The frontier molecular orbitals (MOs), Hirshfeld charge distribution and the Natural bond orbital (NBO) have also been analyzed, which displays the tendency of the ESIPT process. Finally, potential energy curves of the S0 and S1 states were constructed, demonstrating that the ESIPT reaction can be facilitated based on the photo-excitation.
在本工作中，含时密度泛函理论（TDDFT）已被用于研究一种新型发色团II的激发态分子内质子转移（ESIPT）机制[《传感器与执行器B：化学》。202（2014）1190]。计算得到的吸收光谱和荧光光谱与实验结果吻合良好。此外，在第一激发态（S1）中发现了两种类型的II构型，这可归因于ESIPT反应。通过对计算得到的O - H伸缩振动红外（IR）光谱以及氢键能的分析，证实了S1态中氢键的增强。还对前线分子轨道（MOs）、赫希菲尔德电荷分布和自然键轨道（NBO）进行了分析，展示了ESIPT过程的趋势。最后，构建了S0和S1态的势能曲线，表明基于光激发可以促进ESIPT反应。
