Graduate School of Information Science, Nagoya University, Nagoya 464-8601, Japan.
J Chem Phys. 2012 Feb 14;136(6):064519. doi: 10.1063/1.3684239.
A simple model electronic Hamiltonian to describe the potential energy surfaces of several low-lying d-d states of the Fe(bpy)(3) complex is developed for use in molecular dynamics (MD) simulation studies. On the basis of a method proposed previously for first-row transition metal ions in aqueous solution, the model Hamiltonian is constructed using density functional theory calculations for the lowest singlet and quintet states. MD simulations are then carried out for the two spin states in aqueous solution in order to examine the performance of the model Hamiltonian. The simulation results indicate that the present model electronic Hamiltonian reasonably describes the potential energy surfaces of the two spin states of the aqueous Fe(bpy)(3) system, while retaining sufficient simplicity for application in simulation studies on excited state dynamics.
为了在分子动力学 (MD) 模拟研究中使用，我们开发了一个简单的模型电子哈密顿量来描述 [Fe(bpy)(3)] (2+) 配合物的几个低能 d-d 态的势能面。基于先前提出的用于水溶液中第一过渡金属离子的方法，使用密度泛函理论计算构建了模型哈密顿量，用于最低的单线态和五重态。然后在水溶液中对两个自旋态进行 MD 模拟，以检验模型哈密顿量的性能。模拟结果表明，本模型电子哈密顿量合理地描述了水溶液中 [Fe(bpy)(3)] (2+) 体系的两个自旋态的势能面，同时保持足够的简单性，可应用于激发态动力学的模拟研究。
