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American Institute of Physics, The Journal of Chemical Physics, 15(128), p. 154105, 2008

DOI: 10.1063/1.2899649

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Turbo charging time-dependent density-functional theory with Lanczos chains

Journal article published in 2008 by Dario Rocca, Ralph Gebauer, Yousef Saad, Stefano Baroni ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

We introduce a new implementation of time-dependent density-functional theory which allows the \emph{entire} spectrum of a molecule or extended system to be computed with a numerical effort comparable to that of a \emph{single} standard ground-state calculation. This method is particularly well suited for large systems and/or large basis sets, such as plane waves or real-space grids. By using a super-operator formulation of linearized time-dependent density-functional theory, we first represent the dynamical polarizability of an interacting-electron system as an off-diagonal matrix element of the resolvent of the Liouvillian super-operator. One-electron operators and density matrices are treated using a representation borrowed from time-independent density-functional perturbation theory, which permits to avoid the calculation of unoccupied Kohn-Sham orbitals. The resolvent of the Liouvillian is evaluated through a newly developed algorithm based on the non-symmetric Lanczos method. Each step of the Lanczos recursion essentially requires twice as many operations as a single step of the iterative diagonalization of the unperturbed Kohn-Sham Hamiltonian. Suitable extrapolation of the Lanczos coefficients allows for a dramatic reduction of the number of Lanczos steps necessary to obtain well converged spectra, bringing such number down to hundreds (or a few thousands, at worst) in typical plane-wave pseudopotential applications. The resulting numerical workload is only a few times larger than that needed by a ground-state Kohn-Sham calculation for a same system. Our method is demonstrated with the calculation of the spectra of benzene, C$_{60}$ fullerene, and of chlorofyll a.