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Title: Generalized gradient approximation exchange energy functional with correct asymptotic behavior of the corresponding potential

A new non-empirical exchange energy functional of the generalized gradient approximation (GGA) type, which gives an exchange potential with the correct asymptotic behavior, is developed and explored. In combination with the Perdew-Burke-Ernzerhof (PBE) correlation energy functional, the new CAP-PBE (CAP stands for correct asymptotic potential) exchange-correlation functional gives heats of formation, ionization potentials, electron affinities, proton affinities, binding energies of weakly interacting systems, barrier heights for hydrogen and non-hydrogen transfer reactions, bond distances, and harmonic frequencies on standard test sets that are fully competitive with those obtained from other GGA-type functionals that do not have the correct asymptotic exchange potential behavior. Distinct from them, the new functional provides important improvements in quantities dependent upon response functions, e.g., static and dynamic polarizabilities and hyperpolarizabilities. CAP combined with the Lee-Yang-Parr correlation functional gives roughly equivalent results. Consideration of the computed dynamical polarizabilities in the context of the broad spectrum of other properties considered tips the balance to the non-empirical CAP-PBE combination. Intriguingly, these improvements arise primarily from improvements in the highest occupied and lowest unoccupied molecular orbitals, and not from shifts in the associated eigenvalues. Those eigenvalues do not change dramatically with respect to eigenvalues from other GGA-type functionals that do notmore » provide the correct asymptotic behavior of the potential. Unexpected behavior of the potential at intermediate distances from the nucleus explains this unexpected result and indicates a clear route for improvement.« less
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [4]
  1. Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México D. F. 09340, México (Mexico)
  2. (Mexico)
  3. Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, México D. F. 07360, México (Mexico)
  4. Quantum Theory Project, Department of Physics and Department of Chemistry, University of Florida, P.O. Box 118435, Gainesville, Florida 32611-8435 (United States)
Publication Date:
OSTI Identifier:
22416065
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 5; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AFFINITY; APPROXIMATIONS; ASYMPTOTIC SOLUTIONS; BINDING ENERGY; BOND LENGTHS; EIGENVALUES; ELECTRON CORRELATION; FORMATION HEAT; FUNCTIONALS; HYDROGEN; HYDROGEN TRANSFER; IONIZATION POTENTIAL; POLARIZABILITY; POTENTIALS; PROTONS; RESPONSE FUNCTIONS