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Title: Kohn-Sham orbitals and potentials from quantum Monte Carlo molecular densities

In this work we show the possibility to extract Kohn-Sham orbitals, orbital energies, and exchange correlation potentials from accurate Quantum Monte Carlo (QMC) densities for atoms (He, Be, Ne) and molecules (H{sub 2}, Be{sub 2}, H{sub 2}O, and C{sub 2}H{sub 4}). The Variational Monte Carlo (VMC) densities based on accurate Jastrow Antisymmetrised Geminal Power wave functions are calculated through different estimators. Using these reference densities, we extract the Kohn-Sham quantities with the method developed by Zhao, Morrison, and Parr (ZMP) [Phys. Rev. A 50, 2138 (1994)]. We compare these extracted quantities with those obtained form CISD densities and with other data reported in the literature, finding a good agreement between VMC and other high-level quantum chemistry methods. Our results demonstrate the applicability of the ZMP procedure to QMC molecular densities, that can be used for the testing and development of improved functionals and for the implementation of embedding schemes based on QMC and Density Functional Theory.
Authors:
 [1] ;  [2] ;  [3] ;  [4]
  1. Dipartimento di Fisica, Sapienza-Università di Roma, P.le Aldo Moro 5, 00185 Roma (Italy)
  2. Dipartimento di ingegneria e scienze dell'informazione e matematica, Università degli studi dell'Aquila, Via Vetoio, Coppito, 67100 L'Aquila (Italy)
  3. (Italy)
  4. Dipartimento di Scienze Fisiche e Chimiche, Università degli studi dell'Aquila, Via Vetoio, Coppito, 67100 L'Aquila (Italy)
Publication Date:
OSTI Identifier:
22255167
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 5; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CORRELATIONS; DENSITY; DENSITY FUNCTIONAL METHOD; ETHYLENE; HYDROGEN; MONTE CARLO METHOD; WAVE FUNCTIONS