Department of Applied Chemistry, Graduate School of Science and Engineering, University of Toyama, Toyama 930-8555, Japan.
Molecular Spectroscopy Laboratory, RIKEN, Wako 351-0198, Saitama, Japan.
J Am Chem Soc. 2022 Apr 13;144(14):6321-6325. doi: 10.1021/jacs.1c13336. Epub 2022 Apr 4.
Photochemical reactions at the air-water interface can show remarkably different rates from those in bulk water. The present study elucidates the reaction mechanism of phenol characteristic at the air-water interface by the combination of molecular dynamics simulation and quantum chemical calculations of the excited states. We found that incomplete hydrogen bonding to phenol at the air-water interface affects excited states associated with the conical intersection and significantly reduces the reaction barrier, resulting in the distinctively facilitated rate in comparison with the bulk phase. The present study indicates that the reaction dynamics can be substantially different at the interfaces in general, reflecting the difference in the stabilization energy of the electronic states in markedly different solvation at the interface.
在气-水界面上的光化学反应的速率与在体相水中的显著不同。本研究通过分子动力学模拟和激发态量子化学计算的结合，阐明了在气-水界面上具有特征的苯酚反应机理。我们发现，在气-水界面处苯酚的不完全氢键作用会影响与锥形交叉有关的激发态，并显著降低反应势垒，从而导致与体相相比明显加快的反应速率。本研究表明，一般来说，在界面处的反应动力学可能会有很大的不同，这反映了在界面处明显不同的溶剂化条件下电子态的稳定能的差异。
