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

Exchange-correlation potential; Kohn-Sham orbitals; Molecular density; Orbital energy; Quantum chemistry methods; Quantum monte carlo; Reference densities; Variational Monte Carlo; Physics and Astronomy (all); Physical and Theoretical Chemistry

Abstract :

[en] 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 (H2, Be 2, H2O, and C2H4). 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. © 2014 AIP Publishing LLC.

Disciplines :

Physics

Author, co-author :

Varsano, Daniele; Dipartimento di Fisica, Sapienza-Università di Roma, 00185 Roma, Italy ; Centro S3, CNR Istituto di Nanoscienze, 41125 Modena, Italy

BARBORINI, Matteo ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > HPC Platform ; Dipartimento di Ingegneria e Scienze dell'Informazione e Matematica, Università Degli Studi dell'Aquila, 67100 L'Aquila, Italy ; Dipartimento di Scienze Fisiche e Chimiche, Università Degli Studi dell'Aquila, 67100 L'Aquila, Italy

Guidoni, Leonardo; Dipartimento di Scienze Fisiche e Chimiche, Università Degli Studi dell'Aquila, 67100 L'Aquila, Italy

External co-authors :

yes

Language :

English

Title :

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

Publication date :

07 February 2014

Journal title :

Journal of Chemical Physics

ISSN :

0021-9606

eISSN :

1089-7690

Publisher :

American Institute of Physics Inc.

Volume :

140

Issue :

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4863213/15472116/054102_1_online.pdf

Available on ORBilu :

since 04 July 2025

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