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Physical Review Letters

Derivative Discontinuities in Time-Dependent Density-Functional Theory

Michael D. Mundt, Stephan Kümmel

Published Nov 10, 2005• 66 citations
Publisher

Abstract

Based on the Runge-Gross theorem for ensembles we investigate the influence of particle-number-changes on the exchange-correlation potential in time-dependent density-functional theory. We show that the potential changes discontinuously when the particle number crosses an integer value. Real-time simulations of an atomic ionization process demonstrate that this discontinuity appears naturally in the theory of the time-dependent optimized effective potential. The importance of such a discontinuity for physical processes, even such ones in which the particle number is a constant, is discussed.

DOI
10.1103/physrevlett.95.203004

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Based on the Runge-Gross theorem for ensembles we investigate the influence of particle-number-changes on the exchange-correlation potential in time-dependent density-functional theory. We show that the potential changes discontinuously when the particle number crosses an integer value. Real-time simulations of an atomic ionization process demonstrate that this discontinuity appears naturally in the theory of the time-dependent optimized effective potential. The importance of such a discontinuity for physical processes, even such ones in which the particle number is a constant, is discussed.
For every electronic many-body Hamiltonian with a one-body potential that goes to zero at infinity, there is a maximum number of bound electrons (Jmax{J}_{\mathrm{max}}Jmax​) that can be sustained in the system with an infinite lifetime. At this integer Jmax{J}_{\mathrm{max}}Jmax​, the derivative discontinuity in the exact energy of ensemble density functional theory (DFT) is ill defined. However, we investigate the derivative discontinuity of the energy within the framework of density functional resonance theory [D. L. Whitenack and A. Wasserman, Phys. Rev. Lett. 107, 163002 (2011)], which reduces to ground-state DFT as a coordinate scaling parameter is taken to zero, and find that the exact exchange-correlation potential experiences discontinuous jumps at integer particle numbers, including Jmax{J}_{\mathrm{max}}Jmax​. For integers below Jmax{J}_{\mathrm{max}}Jmax​ the jump is purely real because of the real shift in the chemical potential. At Jmax{J}_{\mathrm{max}}Jmax​, the jump has a nonzero imaginary component reflecting the metastability of the system upon addition of one more electron. In addition, the magnitude of the derivative discontinuity at Jmax{J}_{\mathrm{max}}Jmax​ is larger than would have been expected by simply setting the affinity to zero.
Zahariev and Wang [Phys. Rev. A, 70, 042503 (2004)] discuss the density functional theory of noninteger average particle numbers. Among their many results is one we dispute: that the exact exchange-correlation potential (more precisely, the exact functional derivative of the exchange-correlation energy with respect to the density) cannot have a discontinuity as the particle number crosses an integer, in contradiction to works by two of us (J.P.P. and M.L.) in collaboration with co-workers [Phys. Rev. Lett. 49, 1691 (1982); Phys. Rev. Lett.51, 1884 (1983)] and by Sham and Schl\"uter [Phys. Rev. Lett. 51, 1888 (1983)]. We point to a counterexample to Zahariev and Wang's claim, which two of us (E.S. and J.P.P.) have presented in a separate paper: A rigorous proof that, in the absence of external magnetic fields, the exchange-correlation potential jumps by the difference between the ionization potential (I)(I)(I) and electron affinity (A)(A)(A) when the particle number crosses 1, given that $I\ensuremath{\geqslant}A$. We point out that Zahariev and Wang's derivation neglects an order-of-limits problem. We also prove that I>AI>AI>A for any one-electron system in the absence of magnetic fields.
potential of an open system may jump discontinuously as the particle number crosses an integer, with important physical consequences. Recently, Sagvolden and Perdew (Phys Rev A 2008, 77, 012517) have analyzed the discontinuity of the exchange-correlation potential as the particle number crosses one, with an illustration that uses a model density for the H � ion. In this work, we extend their analysis to the case in which the external potential is the simple harmonic confinement, choosing spring-constant values for which the two-electron hamiltonian has an analytic solution. This way, we can obtain the exact, analytic, exchange and correlation potentials for particle number fluctuating between zero and two, illustrating the discontinuity as the particle number crosses one without introducing any model or approximation. We also discuss exchange and correlation separately. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 2410–2415, 2009 Key words: density functional theory; electronic correlation; exchange-correlation potentials; harmonic traps
The Runge-Gross [E. Runge and E. K. U. Gross, Phys. Rev. Lett. 52, 997 (1984)] action functional of time-dependent density-functional theory leads to a well-known causality paradox; that is, a perturbation of the electronic density in the future affects the response of the system in the present. This paradox is known to be caused by an inconsistent application of the Dirac-Frenkel variational principle. In view of the recent solutions to this problem, the action functional employed by Runge and Gross in their formulation of time-dependent density-functional theory is analyzed in the context of the Keldysh contour technique. The time-dependent electronic density and the concept of causality are extended to the contour. We derive a variational equation that obeys causality and relates the exchange-correlation potential with its kernel and the functional derivative of the exchange-correlation action functional with respect to the density. It is shown that the adiabatic local-density approximation is a consistent solution of this equation and that the time-dependent optimized potential method can also be derived from it. The formalism presented here can be used to find new approximation methods for the exchange-correlation potential and to avoid the causality dilemma.
We investigate when Taylor expansions can be used to prove the Runge-Gross theorem, which is at the foundation of time-dependent density-functional theory (TDDFT). We start with a general analysis of the conditions for the Runge-Gross argument, especially the time differentiability of the density. The latter should be questioned in the presence of singular (e.g., Coulomb) potentials. Then we show that a singular potential in a one-body operator considerably decreases the class of time-dependent external potentials to which the original argument can be applied. A two-body singularity has an even stronger impact and an external potential is essentially incompatible with it. For the Coulomb interaction and all reasonable initial many-body states, the Taylor expansion only exists to a finite order, except for constant external potentials. Therefore, high-order Taylor expansions are not the right tool to study atoms and molecules in TDDFT.