Harbola and Sahni reply

Harbola, Manoj K.; Sahni, Viraht

doi:10.1103/physrevlett.65.277

Cited by 56 publications

(84 citation statements)

References 10 publications

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“…The treatment of the excited states within the DFT is a more recent development. [9][10][11][12][13][14][15] The essential element of DFT is the input of the exchange-correlation energy functional whose exact form is unknown. The simplest approximation for the xc-energy functional is through the local spin-density approximation 1,16 ͑LSDA͒ of homogeneous electronic gas.…”

Section: Introductionmentioning

confidence: 99%

Recent development of self-interaction-free time-dependent density-functional theory for nonperturbative treatment of atomic and molecular multiphoton processes in intense laser fields

Chu¹

2005

The Journal of Chemical Physics

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A critical re-assignment of the Rydberg states of iodomethane based on new polarization data J. Chem. Phys. 138, 134308 (2013) In this paper, we present a short account of some recent developments of self-interaction-free density-functional theory ͑DFT͒ and time-dependent density-functional theory ͑TDDFT͒ for accurate and efficient treatment of the electronic structure, and time-dependent quantum dynamics of many-electron atomic and molecular systems. The conventional DFT calculations using approximate and explicit exchange-correlation energy functional contain spurious self-interaction energy and improper long-range asymptotic potential, preventing reliable treatment of the excited, resonance, and continuum states. We survey some recent developments of DFT/TDDFT with optimized effective potential ͑OEP͒ and self-interaction correction ͑SIC͒ for both atomic and molecular systems for overcoming some of the above mentioned difficulties. These DFT ͑TDDFT͒/ OEP-SIC approaches allow the use of orbital-independent single-particle local potential which is self-interaction free. In addition we discuss several numerical techniques recently developed for efficient and high-precision treatment of the self-interaction-free DFT/TDDFT equations. The usefulness of these procedures is illustrated by a few case studies of atomic, molecular, and condensed matter processes of current interests, including ͑a͒ autoionizing resonances, ͑b͒ relativistic OEP-SIC treatment of atomic structure ͑Z = 2-106͒, ͑c͒ shell-filling electronic structure in quantum dots, ͑d͒ atomic and molecular processes in intense laser fields, including multiphoton ionization, and very-high-order harmonic generation, etc. For the time-dependent processes, an alternative Floquet formulation of TDDFT is introduced for time-independent treatment of multiphoton processes in intense periodic or quasiperiodic fields. We conclude this paper with some open questions and perspectives of TDDFT.

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Section: Introductionmentioning

confidence: 99%

Recent development of self-interaction-free time-dependent density-functional theory for nonperturbative treatment of atomic and molecular multiphoton processes in intense laser fields

Chu¹

2005

The Journal of Chemical Physics

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“…To eliminate any ambiguity caused by possible flaws in the analytical fit ͑14͒, we also used directly the F͓s(r)͔ and dF/ds from Hartree-Fock ͑HF͒ in Eq. ͑13͒, again finding that the eigenvalues 9 are not improved. This demonstrates that the failure to reproduce the correct eigenvalues is an intrinsic flaw of the exchange functional ͑11͒ used with GGA.…”

Section: To Determine F(s) We Calculated F(r)ϭementioning

confidence: 93%

Generalized generalized gradient approximation:An improved density-functional theory for accurate orbital eigenvalues

1997

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The generalized gradient approximation ͑GGA͒ for the exchange functional in conjunction with accurate expressions for the correlation functional have led to numerous applications in which density-functional theory ͑DFT͒ provides structures, bond energies, and reaction activation energies in excellent agreement with the most accurate ab initio calculations and with the experiment. However, the orbital energies that arise from the Kohn-Sham auxiliary equations of DFT may differ by a factor of 2 from the ionization potentials, indicating that excitation energies and properties involving sums over excited states ͑nonlinear-optical properties, van der Waals attraction͒ may be in serious error. We propose herein a generalization of the GGA in which the changes in the functionals due to virtual changes in the orbitals are allowed to differ from the functional used to map the exact density onto the exact energy. Using the simplest version of this generalized GGA we show that orbital energies are within ϳ5% of the correct values and the long-range behavior has the correct form.

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“…Many different schemes have been proposed to address the selfinteraction error, some well-known examples include ͑i͒ an explicit orbital-dependent correction that removes the surplus electrostatic term ͑sic correction͒; 4,5 ͑ii͒ interpolating the DFT functional with the self-interaction free HartreeFock exchange energy ͑hybrid functionals͒; 6,7 and ͑iii͒ directly modifying the KS potential to make it reproduce essential features of exact exchange. [8][9][10][11][12][13] However, none of these schemes provide a general treatment of this error within an unaltered semilocal DFT framework. Another observation of the difficulty for XC functionals to deal with systems with electrons confined in space can be made in that functionals which are not specifically oriented toward quantum chemistry ͑e.g., by fitting to atoms and small molecules͒ often have trouble with such systems ͑see, e.g., Ref.…”

Section: Introductionmentioning

confidence: 99%

Subsystem functionals and the missing ingredient of confinement physics in density functionals

2010

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The subsystem functional scheme is a promising approach recently proposed for constructing exchangecorrelation density functionals. In this scheme, the physics in each part of real materials is described by mapping to a characteristic model system. The "confinement physics," an essential physical ingredient that has been left out in present functionals, is studied by employing the harmonic-oscillator ͑HO͒ gas model. By performing the potential→ density and the density→ exchange energy per particle mappings based on two model systems characterizing the physics in the interior ͑uniform electron-gas model͒ and surface regions ͑Airy gas model͒ of materials for the HO gases, we show that the confinement physics emerges when only the lowest subband of the HO gas is occupied by electrons. We examine the approximations of the exchange energy by several state-of-the-art functionals for the HO gas, and none of them produces adequate accuracy in the confinement dominated cases. A generic functional that incorporates the description of the confinement physics is needed.

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Harbola and Sahni reply

Cited by 56 publications

References 10 publications

Recent development of self-interaction-free time-dependent density-functional theory for nonperturbative treatment of atomic and molecular multiphoton processes in intense laser fields

Recent development of self-interaction-free time-dependent density-functional theory for nonperturbative treatment of atomic and molecular multiphoton processes in intense laser fields

Generalized generalized gradient approximation:An improved density-functional theory for accurate orbital eigenvalues

Subsystem functionals and the missing ingredient of confinement physics in density functionals

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