Time-dependent density functional theory (Q2503438): Difference between revisions

Over the last three decades, the density functional theory (DFT), that is underlain by the celebrated Hohenberg-Kohn (HK) theorem and the Kohn-Sham self-consistent field method, has become an extraordinarily popular computational method in condensed matter physics and quantum chemistry and has significantly influenced the state of art of quantum theory of atoms, molecules, clusters, and solids (recently, the reduction ad absurdum proof of the HK theorem has been revisited by \textit{E. S. Kryachko} [Int. J. Quantum Chem. 103, 818 (2005); ibid. 106, 1795 (2006)]) in connection with the well-known Kato cusp condition for many-electron Coulomb systems [\textit{T. Kato}, Commun. Pure Appl. Math. 10, 151--177 (1957; Zbl 0077.20904)]. In 1984, Runge and Gross proved the time-dependent analog of the HK theorem stating that, under certain quite general conditions, there exists a one-to-one correspondence between time-dependent one-electron densities \(\rho(\mathbf{r},t)\) and time-dependent one-body external potentials \(v_{ext}({\mathbf r},t)\), for a given initial state. Put in other words, a given evolution of the one-electron density can be generated by at most one time-dependent external potential. One can further define a fictitious system of noninteracting electrons, whose density is identical to that of the real system, as moving in a time-dependent KS effective potential. The latter, by analogy with the DFT, is decomposed into an external part, the Hartree potential, and the exchange-correlation potential \(v_{xc}({\mathbf r},t)\) which ``absorbs'' the entire history of the one-electron density \(\rho({\mathbf r},t)\) and whose precise form is unknown. Altogether, this underlies the time-dependent density functional theory (TD DFT) that has become a popular method in the last decade to calculate, at relatively modest computational expense, electronic excitation energies and response properties of solids, clusters, and molecules. Since any theory cannot be absolutely perfect, this is also true for the TD DFT, as though the latter has always been considered as a formally exact theory in the sense that it is exact iff the exact time-dependent exchange-correlation potential is explicitly known, and all its encountered imperfectness has been interpreted in terms of the imperfect knowledge of the latter potential. The foundations of the TD DFT have recently been reexamined by \textit{J. Schirmer} and \textit{A. Dreuw} [Phys. Rev. A 75, 022513 (2007)]. The reviewed book is a broad reflection of the current state of the TD DFT and summary of its achievements since 1984. It is naturally partitioned into the Chapters that outline the formal theoretical approach of the TD DFT, the methods of approximating \(v_{xc}({\mathbf r},t)\), the numerical and application aspects of the TD DFT, and its new frontiers. The theoretical approach is provided by the following Chapters: ``Beyond the Runge-Gross Theorem'', ``Introduction to the Keldysh Formalism'', ``Initial-State Dependence and Memory'', ``Current Density Functional Theory'', ``Multicomponent Density-Functional Theory'', and ``Intermolecular Forces and Generalized Response Functions in Liouville Space''. The methods of approximating the exchange-correlation potential are discussed in the Chapters entitled ``Time-Dependent Deformation Approximation'', ``Exact-Exchange Methods and Perturbation Theory along the Adiabatic Connection'', ``Approximate Functionals from Many-Body Perturbation Theory'', and ``Exact Conditions''. The numerical aspects of the TD DFT are discussed in the following Chapters: ``Propagators for the Time-Dependent Kohn-Sham Equations'', ``Solution of the Linear-Response Equations in a Basis Set'', ``Excited-State Dynamics in Finite Systems and Biomolecules'', and ``Time Versus Frequency Space Techniques''. The list of Chapters on the TD DFT applications split into those which deal with the linear response regime and those beyond. The former list covers such themes as open-shell molecules, atoms and clusters, semiconductor nanostructures, solids, polymers, biochromophores, whereas the latter is dedicated to atoms, molecules, and clusters in strong laser fields. The Chapters gathered together as ``New Frontiers'' discuss the relation between the TD DFT and van der Waals forces, transport properties, and scattering. To summarize, the book ``Time-Dependent Density Functional Theory'' is a valuable book for those, PhD students in particular, who are interested in the whole spectrum of problems related to density functional theory and its broad applications to many-body quantum theory.