期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 31, 页码 20976-20985出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp00722h
关键词
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资金
- National Science Foundation [CHE-1152784]
- Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences [DE-SC0008623]
- FWF (Austrian Science Fund) [P 25739-N27]
- Austrian Science Fund (FWF) [P 25739] Funding Source: researchfish
- U.S. Department of Energy (DOE) [DE-SC0008623] Funding Source: U.S. Department of Energy (DOE)
When running time-dependent density functional theory (TDDFT) calculations for real-time simulations of non-equilibrium dynamics, the user has a choice of initial Kohn-Sham state, and typically a Slater determinant is used. We explore the impact of this choice on the exchange-correlation potential when the physical system begins in a 50 : 50 superposition of the ground and first-excited state of the system. We investigate the possibility of judiciously choosing a Kohn-Sham initial state that minimizes errors when adiabatic functionals are used. We find that if the Kohn-Sham state is chosen to have a configuration matching the one that dominates the interacting state, this can be achieved for a finite time duration for some but not all such choices. When the Kohn-Sham system does not begin in a Slater determinant, we further argue that the conventional splitting of the exchange-correlation potential into exchange and correlation parts has limited value, and instead propose a decomposition into a single-particle'' contribution that we denote v(xc)(S), and a remainder. The single-particle contribution can be readily computed as an explicit orbital-functional, reduces to exchange in the Slater determinant case, and offers an alternative to the adiabatic approximation as a starting point for TDDFT approximations.
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