School of Energy and Environment , City University of Hong Kong , Hong Kong Special Administrative Region , People's Republic of China.
J Chem Theory Comput. 2019 Sep 10;15(9):4781-4789. doi: 10.1021/acs.jctc.9b00281. Epub 2019 Aug 7.
We propose a new constrained density functional theory (CDFT) approach which directly controls the oxidation state of the target atoms. In this new approach called oxidation-state constrained density functional theory (OS-CDFT), the eigenvalues of the occupation matrix obtained from projecting the Kohn-Sham wave functions onto the valence orbitals are constrained to obtain the desired oxidation states. This approach is particularly useful to study electron transfer problems in transition metal-containing systems due to the multivalent nature of the transition metal ions. The calculation of the forces on the ions and of the coupling constant was implemented under the OS-CDFT scheme to allow efficient and accurate study of electron transfer reactions. We demonstrated the application of this method in the study of different electron transfer reactions including the aqueous ferrous-ferric self-exchange reaction, polaron hopping in the TiO anatase and bismuth vanadate, and photoexcited electron transfer in the sapphire.
我们提出了一种新的受限密度泛函理论（CDFT）方法，该方法可以直接控制目标原子的氧化态。在这种称为氧化态受限密度泛函理论（OS-CDFT）的新方法中，通过将 Kohn-Sham 波函数投影到价轨道上来获得占据矩阵的本征值，从而获得所需的氧化态。由于过渡金属离子的多价性质，该方法特别适用于研究含过渡金属体系中的电子转移问题。在 OS-CDFT 方案下，对离子的力和耦合常数的计算得到了实现，从而可以有效地和准确地研究电子转移反应。我们展示了该方法在不同电子转移反应中的应用，包括水溶液中亚铁-铁自交换反应、TiO2 锐钛矿和 BiVO4 中的极化子跳跃以及蓝宝石中的光激发电子转移。
