Hydrogen Bonding Dynamics of Phenol-(H

Journal of the Korean Chemical Society

Hong Dong¹  Ce Hao¹  Jieshan Qiu¹  Se Wang¹  Dandan Wang¹ 

关键词: Hydrogen bond;    Excited state;    Electronic spectra;    Vibrational spectra;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The time-dependent density functional theory (TDDFT) method has been carried out to investigate the excitedstate hydrogen-bonding dynamics of phenol-(H2O)2 complex. The geometric structures and infrared (IR) spectra in ground state and different electronically excited states (S1 and T1) of the hydrogen-bonded complex have been calculated using the density functional theory (DFT) and TDDFT method. A ring of three hydrogen bonds is formed between phenol and two water molecules. We have demonstrated that the intermolecular hydrogen bond O1-H2¡¤¡¤¡¤O3-H of the three hydrogen bonds is strengthened in S1 and T1 states. In contrast, the hydrogen bond O5-H6¡¤¡¤¡¤O1-H is weakened in S1 and T1 states. These results are obtained by theoretically monitoring the changes of the bond lengths of the hydrogen bonds and hydrogen-bonding groups in different electronic states. The hydrogen bond O1-H2¡¤¡¤¡¤O3-H strengthening in both the S1 and T1 states is confirmed by the calculated stretching vibrational mode of O-H (phenol) being red-shifted upon photoexcitation. The hydrogen bond strengthening and weakening behavior in electronically excited states may exist in other ring structures of phenol-(H2O)n.

【 授权许可】

Unknown