Department of Physics and Astronomy, Hunter College and the Graduate Center of the City University of New York, 695 Park Avenue, New York, New York 10065, USA.
Phys Rev Lett. 2012 Dec 28;109(26):266404. doi: 10.1103/PhysRevLett.109.266404. Epub 2012 Dec 26.
We show that the exact exchange-correlation potential of time-dependent density-functional theory displays dynamical step structures that have a spatially nonlocal and time nonlocal dependence on the density. Using one-dimensional two-electron model systems, we illustrate these steps for a range of nonequilibrium dynamical situations relevant for modeling of photochemical or physical processes: field-free evolution of a nonstationary state, resonant local excitation, resonant complete charge transfer, and evolution under an arbitrary field. A lack of these steps in the usual approximations yields inaccurate dynamics, for example, predicting faster dynamics and incomplete charge transfer.
我们表明，含时密度泛函理论的精确交换关联势具有动力学阶跃结构，其对密度的空间非局域性和时间非局域性依赖。我们使用一维双电子模型系统，说明了这些阶跃结构在一系列与光化学或物理过程建模相关的非平衡动力学情况下的情况：非定态的无场演化、共振局域激发、共振完全电荷转移以及任意场下的演化。通常的近似方法中缺少这些阶跃结构会导致动力学不准确，例如，预测更快的动力学和不完全的电荷转移。
