Discontinuities of the exchange-correlation kernel and charge-transfer excitations in time-dependent density functional theory

Abstract

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 which diverges as $r\to \infty$. 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.

6 pages, 3 figures (expanded version, accepted in Phys. Rev. A)

References in corpus (2)

• Conserving Approximations in Time-Dependent Density Functional Theory
• Linear density response function within the time-dependent exact-exchange approximation

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