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Excitation energies from time‐dependent density functional theory using exact and approximate potentials
Author(s) -
Petersilka M.,
Gross E. K. U.,
Burke Kieron
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/1097-461x(2000)80:4/5<534::aid-qua3>3.0.co;2-v
Subject(s) - excitation , local density approximation , density functional theory , time dependent density functional theory , atomic physics , rydberg formula , ground state , hybrid functional , adiabatic process , chemistry , physics , quantum mechanics , ionization , ion
The role of the exchange–correlation potential and the exchange–correlation kernel in the calculation of excitation energies from time‐dependent density functional theory is studied. Excitation energies of the helium and beryllium atoms are calculated, both from the exact Kohn–Sham ground‐state potential and from two orbital‐dependent approximations. These are exact exchange and self‐interaction corrected local density approximation (SIC‐LDA), both calculated using Krieger–Li–Iafrate approximation. For the exchange–correlation kernels, three adiabatic approximations were tested: the local density approximation, exact exchange, and SIC‐LDA. The choice of the ground‐state exchange–correlation potential has the largest impact on the absolute position of most excitation energies. In particular, orbital‐dependent approximate potentials result in a uniform shift of the transition energies to the Rydberg states. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 534–554, 2000