Departamento de Física and IFIBA, FCEN, Universidad de Buenos Aires, Ciudad Universitaria, Pab. I, C1428EHA Ciudad de Buenos Aires, Argentina.
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 Chem Chem Phys. 2018 Nov 7;20(41):26145-26160. doi: 10.1039/c8cp03957g. Epub 2018 Oct 12.
A decomposition of the exact exchange-correlation potential of time-dependent density functional theory into an interaction component and a kinetic component offers a new starting point for non-adiabatic approximations. The components are expressed in terms of the exchange-correlation hole and the difference between the one-body density matrix of the interacting and Kohn-Sham systems, which must be approximated in terms of quantities accessible from the Kohn-Sham evolution. We explore several preliminary approximations, evaluate their fulfillment of known exact conditions, and test their performance on simple model systems for which available exact solutions indicate the significance of going beyond the adiabatic approximation.
将含时密度泛函理论的精确交换关联势分解为相互作用部分和动力学部分，为非绝热近似提供了新的起点。这些分量可以表示为交换关联空洞和相互作用体系与 Kohn-Sham 体系的单粒子密度矩阵之间的差值，而这些差值必须根据 Kohn-Sham 演化中可得到的量来近似。我们探索了几种初步的近似方法，评估了它们满足已知精确条件的程度，并在简单的模型体系上测试了它们的性能，这些模型体系的精确解表明超越绝热近似的重要性。
