Theory Department
Max Planck Institute of Microstructure Physics
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Hellgren, M., Gross, E. K. U.

Discontinuities of the exchange-correlation kernel and charge transfer excitations in time-dependent density-functional theory
Physical Review A 85, (2),pp 022514/1-6 (2012)
We identify the key property that the exchange-correlation (XC) kernel of time-dependent density-functional theory must have in order to describe long-range charge-transfer excitations. We show that the discontinuity of the XC potential as a function of particle number induces a space- and frequency-dependent discontinuity of the XC kernel that diverges as r -> ∞. In a combined donor-acceptor system, the same discontinuity compensates for the vanishing overlap between the acceptor and donor orbitals, thereby yielding a finite correction to the Kohn-Sham eigenvalue differences. This mechanism is illustrated to first order in the Coulomb interaction.

Th-2012-12