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Physical Review A

Sum rules and properties in time-dependent density-functional theory

Zhixin Qian, Viraht Sahni

Published Mar 19, 2001• 23 citations
Publisher

Abstract

Time-dependent quantal density-functional theory (Q-DFT) is a description of the s-system of noninteracting fermions with electronic density equivalent to that of Schr\"odinger theory, in terms of fields whose sources are quantum-mechanical expectations of Hermitian operators. The theory delineates and defines the contribution of each type of electron correlation to the local electron-interaction potential ${\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)$ of the s system. These correlations are due to the Pauli exclusion principle, Coulomb repulsion, correlation-kinetic, and correlation-current-density effects, the latter two resulting, respectively, from the difference in kinetic energy and current density between the interacting Schr\"odinger and noninteracting systems. We employ Q-DFT to prove the following sum rules and properties of the s system: (i) the components of the potential due to these correlations separately exert no net force on the system; (ii) the torque of the potential is finite and due solely to correlation-current-density effects; (iii) two sum rules involving the curl of the dynamic electron-interaction kernel defined as the functional derivative of ${\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)$ are derived and shown to depend on the frequency dependent correlation-current-density effect. Furthermore, via adiabatic coupling constant (\ensuremath{\lambda}) perturbation theory, we prove: (iv) the exchange potential ${\ensuremath{\nu}}_{x}(\mathbf{r},t)$ is the work done in a conservative field representative of Pauli correlations and lowest-order $O(\ensuremath{\lambda})$ correlation-kinetic and correlation-current-density effects; (v) the correlation potential ${\ensuremath{\nu}}_{c}(\mathbf{r},t)$ commences in $O({\ensuremath{\lambda}}^{2}),$ and, at each order, it is the work done in a conservative field representative of Coulomb correlations and correlation-kinetic and correlation-current-density effects; (vi) we derive the integral virial theorem relating ${\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)$ to the electron-interaction and correlation-kinetic energy for arbitrary coupling constant strength \ensuremath{\lambda}, and show there are no explicit correlation-current-density contributions to the energy. From this integral virial theorem we (vii) obtain the fully interacting $(\ensuremath{\lambda}=1)$ and exchange-only $(\ensuremath{\lambda}=0)$ integral virial theorems as special cases, the latter showing there is no explicit correlation-kinetic contribution to the exchange energy; and (viii) write expressions for the electron-interaction and correlation-kinetic actions for arbitrary coupling constant \ensuremath{\lambda} in terms of the corresponding fields.

DOI
10.1103/physreva.63.042508

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Time-dependent quantal density-functional theory (Q-DFT) is a description of the s-system of noninteracting fermions with electronic density equivalent to that of Schr"odinger theory, in terms of fields whose sources are quantum-mechanical expectations of Hermitian operators. The theory delineates and defines the contribution of each type of electron correlation to the local electron-interaction potential \ensuremathνee(r,t){\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)\ensuremathνee​(r,t) of the s system. These correlations are due to the Pauli exclusion principle, Coulomb repulsion, correlation-kinetic, and correlation-current-density effects, the latter two resulting, respectively, from the difference in kinetic energy and current density between the interacting Schr"odinger and noninteracting systems. We employ Q-DFT to prove the following sum rules and properties of the s system: (i) the components of the potential due to these correlations separately exert no net force on the system; (ii) the torque of the potential is finite and due solely to correlation-current-density effects; (iii) two sum rules involving the curl of the dynamic electron-interaction kernel defined as the functional derivative of \ensuremathνee(r,t){\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)\ensuremathνee​(r,t) are derived and shown to depend on the frequency dependent correlation-current-density effect. Furthermore, via adiabatic coupling constant (\ensuremath{\lambda}) perturbation theory, we prove: (iv) the exchange potential \ensuremathνx(r,t){\ensuremath{\nu}}_{x}(\mathbf{r},t)\ensuremathνx​(r,t) is the work done in a conservative field representative of Pauli correlations and lowest-order O(\ensuremathλ)O(\ensuremath{\lambda})O(\ensuremathλ) correlation-kinetic and correlation-current-density effects; (v) the correlation potential \ensuremathνc(r,t){\ensuremath{\nu}}_{c}(\mathbf{r},t)\ensuremathνc​(r,t) commences in O(\ensuremathλ2),O({\ensuremath{\lambda}}^{2}),O(\ensuremathλ2), and, at each order, it is the work done in a conservative field representative of Coulomb correlations and correlation-kinetic and correlation-current-density effects; (vi) we derive the integral virial theorem relating \ensuremathνee(r,t){\ensuremath{\nu}}_{\mathrm{ee}}(\mathbf{r},t)\ensuremathνee​(r,t) to the electron-interaction and correlation-kinetic energy for arbitrary coupling constant strength \ensuremath{\lambda}, and show there are no explicit correlation-current-density contributions to the energy. From this integral virial theorem we (vii) obtain the fully interacting (\ensuremathλ=1)(\ensuremath{\lambda}=1)(\ensuremathλ=1) and exchange-only (\ensuremathλ=0)(\ensuremath{\lambda}=0)(\ensuremathλ=0) integral virial theorems as special cases, the latter showing there is no explicit correlation-kinetic contribution to the exchange energy; and (viii) write expressions for the electron-interaction and correlation-kinetic actions for arbitrary coupling constant \ensuremath{\lambda} in terms of the corresponding fields.
Local effective potential theory of electronic structure is the mapping from a system of electrons in an external field to one of noninteracting fermions or bosons with the same electronic density. The energy and ionization potential are also thereby determined. The mappings may be achieved via either quantal density-functional theory (QDFT) or Hohenberg-Kohn-Sham density-functional theory (HKS-DFT). The wave function for the model fermionic system is a Slater determinant of spin orbitals, whereas that for the model bosons is the density amplitude. In the QDFT mappings, the contributions of the electron correlations due to the Pauli exclusion principle, Coulomb repulsion and correlation-kinetic effects are separately delineated. It has been proved via QDFT that the contribution of Pauli and Coulomb correlations to these model systems is the same; the difference lies solely in their correlation-kinetic component. In this paper, we apply the QDFT of the density amplitude to study the mapping to the bosonic model. The application is to atoms and performed at the Hartree-Fock theory level of electron correlations. A principal conclusion is that correlation-kinetic effects play a significant role in the mapping to the bosonic model, whereas they are negligible in the mapping to the model fermions. For the bosonic model, this contribution increases with electron number, becoming nearly as significant as those due to the corresponding electron-interaction (the sum of the Hartree and Pauli) term. The significance of the correlation-kinetic effects will be further enhanced on the inclusion of Coulomb correlations and the corresponding correlation-kinetic contributions. The consequences of these conclusions for the HKS-DFT of the density amplitude are discussed, as are directions for future work.
Local effective potential theory, both stationary-state and time-dependent, constitutes the mapping from a system of electrons in an external field to one of the noninteracting fermions possessing the same basic variable such as the density, thereby enabling the determination of the energy and other properties of the electronic system. This paper is a description via Quantal Density Functional Theory (QDFT) of the electron correlations that must be accounted for in such a mapping. It is proved through QDFT that independent of the form of external field, (a) it is possible to map to a model system possessing all the basic variables; and that (b) with the requirement that the model fermions are subject to the same external fields, the only correlations that must be considered are those due to the Pauli exclusion principle, Coulomb repulsion, and Correlation–Kinetic effects. The cases of both a static and time-dependent electromagnetic field, for which the basic variables are the density and physical current density, are considered. The examples of solely an external electrostatic or time-dependent electric field constitute special cases. An efficacious unification in terms of electron correlations, independent of the type of external field, is thereby achieved. The mapping is explicated for the example of a quantum dot in a magnetostatic field, and for a quantum dot in a magnetostatic and time-dependent electric field.
Abstract The quantal density functional theory (Q‐DFT) of excited states is the description of the physics of the mapping from any bound nondegenerate excited state of Schrödinger theory to that of the s‐system of noninteracting Fermions with equivalent density ρk(r), energy Ek, and ionization potential Ik. The s‐system may either be in an excited state with the same configuration as in Schrödinger theory or in a ground state with a consequently different configuration. The Q‐DFT description of the s‐system is in terms of a conservative field ℱk(r), whose electron‐interaction ℰee(r) and correlation‐kinetic 𝒵 (r) components are separately representative of electron correlations due to the Pauli exclusion principle and Coulomb repulsion, and correlation‐kinetic effects, respectively. The sources of these fields are expectations of Hermitian operators taken with respect to the system wavefunction. The local electron‐interaction potential vee(r) of the s‐system, representative of all the many‐body correlations, is the work done to move an electron in the force of the field ℱk(r). The electron interaction Eee and correlation‐kinetic Tc components of the total energy Ek may be expressed in integral virial form in terms of their respective fields. The difference between the s‐system in its ground or excited state representation is due entirely to correlation‐kinetic effects. The highest occupied eigenvalue of the s‐system differential equation in either case is minus the ionization potential Ik. In this work we demonstrate the transformation of an excited state of Schrödinger theory, as represented by the first excited singlet state of the exactly solvable Hooke's atom, to that of noninteracting Fermions in their ground state with equivalent excited state density, energy, and ionization potential. To further prove the Fermions are in a ground state, we solve the corresponding singlet s‐system differential equation numerically for the vee(r) determined, and obtain the excited state density from the zero node orbitals generated. The resulting total energy is also the same. In addition, the single eigenvalue determined corresponds to minus the ionization potential of the excited state. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001
The formally exact expression of the exchange-correlation potential in the local-scaling density functional theory (LSDFT) was derived recently by the author, and it is equivalent to that of Holas and March. The basic equation of the LS-DFT was also derived, and it is equivalent to the differential virial theorem (DVT). The LS-DFT has been extended to the local-scaling current density functional theory (LS-CDFT). This has been compared with the formulation of Holas and March. In this note, the LS-CDFT is extended to the timedependent system; i.e., the local-scaling time-dependent current density functional theory (LS-TDCDFT) is formulated. As a straightforward extension of ref. 3, the density and the paramagnetic current density jp are adopted as the basic variables, which is the same procedure used by Colwell et al. It is explicitly shown that the time-dependent exchange-correlation scalar potential vxc and the vector one Axc are same functionals of firstand second-order density matrices as those of the time-independent case, while the total effective potentials are not so. The equation of motion of jp provides the DVT for the time-dependent system in the magnetic field. The time-dependent term of the DVT is equal to that of the nonmagnetic time-dependent system. Throughout the entire formulation, the notation of the tensor product is suppressed. Here, an N-electron system in an external scalar potential vextðr; tÞ, an external vector potential Aextðr; tÞ, and an interaction potential uðr; r0Þ 1⁄4 =jr r0j is considered, where is the coupling constant treated as a variable parameter. In a time-independent theory, the quantity to be minimized is the energy. But in the time-dependent case, the action S plays the role:
Time-dependent orbital-free density functional theory (DFT) is an efficient method for calculating the dynamic properties of large-scale quantum systems due to the low computational cost compared to standard time-dependent DFT. We formalize this method by mapping the real system of interacting fermions onto a fictitious system of noninteracting bosons. The dynamic Pauli potential and associated kernel emerge as key ingredients of time-dependent orbital-free DFT. Using the uniform electron gas as a model system, we derive an approximate frequency-dependent Pauli kernel. Pilot calculations suggest that space nonlocality is a key feature for this kernel. Nonlocal terms arise already in the second-order expansion with respect to unitless frequency and reciprocal space variable ($\frac{\ensuremath{\omega}}{q\phantom{\rule{0.16em}{0ex}}{k}_{F}}$ and q2kF\frac{q}{2\phantom{\rule{0.16em}{0ex}}{k}_{F}}2kF​q​, respectively). Given the encouraging performance of the proposed kernel, we expect it will lead to more accurate orbital-free DFT simulations of nanoscale systems out of equilibrium. Additionally, the proposed path to formulate nonadiabatic Pauli kernels presents several avenues for further improvements which can be exploited in future work to improve the results.