화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.119, No.25, 8104-8114, 2015
Theoretical Study of Proton Coupled Electron Transfer Reactions: The Effect of Hydrogen Bond Bending Motion
We investigate theoretically the effect of hydrogen,bond bending Motion on the proton coupled electron transfer (PCET) reaction, using,a model system where an intramolecular hydrogen-bonded phenol group is the proton, donor. It is shown that, in a two-dimensional (2D) model of the PCET reaction, the bending and stretching vibrational motions are separated, and due to the hydrogen bond configuration and anharmonicity :of the potential energy surface, the bending vibration can play a role in the PCET reaction. The results are also compared With two different sets of one-dimensional models (ID-linear and ID-curved). Due to contributions of the bending motion, the rate constants in the 2D model are larger than those in the ID-linear model, although the differences between the total rate constants and KIEs for 2D and 1D models are not major. Results from the 1D-curved model lie between the 2D- and ID-linear models, indicating that it can include softie effect of bending motion in reducing the potential energies along the reaction path.