TY - JOUR

T1 - Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals

A1 - Hammer,Bjørk

A1 - Hansen,Lars Bruno

A1 - Nørskov,Jens Kehlet

AU - Hammer,Bjørk

AU - Hansen,Lars Bruno

AU - Nørskov,Jens Kehlet

PY - 1999

Y1 - 1999

N2 - A simple formulation of a generalized gradient approximation for the exchange and correlation energy of electrons has been proposed by Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)]. Subsequently Zhang and Yang [Phys. Rev. Lett. 80, 890 (1998)] have shown that a slight revision of the PBE functional systematically improves the atomization energies for a large database of small molecules. In the present work, we show that the Zhang and Yang functional (revPBE) also improves the chemisorption energetics of atoms and molecules on transition-metal surfaces. Our test systems comprise atomic and molecular adsorption of oxygen, CO, and NO on Ni(100), Ni(111), Rh(100), Pd(100), and Pd(111) surfaces. As the revPBE functional may locally violate the Lieb-Oxford criterion, we further develop an alternative revision of the PBE functional, RPBE, which gives the same improvement of the chemisorption energies as the revPBE functional at the same time as it fulfills the Lieb-Oxford criterion locally. [S0163-1829(99)02711-3].

AB - A simple formulation of a generalized gradient approximation for the exchange and correlation energy of electrons has been proposed by Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)]. Subsequently Zhang and Yang [Phys. Rev. Lett. 80, 890 (1998)] have shown that a slight revision of the PBE functional systematically improves the atomization energies for a large database of small molecules. In the present work, we show that the Zhang and Yang functional (revPBE) also improves the chemisorption energetics of atoms and molecules on transition-metal surfaces. Our test systems comprise atomic and molecular adsorption of oxygen, CO, and NO on Ni(100), Ni(111), Rh(100), Pd(100), and Pd(111) surfaces. As the revPBE functional may locally violate the Lieb-Oxford criterion, we further develop an alternative revision of the PBE functional, RPBE, which gives the same improvement of the chemisorption energies as the revPBE functional at the same time as it fulfills the Lieb-Oxford criterion locally. [S0163-1829(99)02711-3].

KW - METAL-SURFACES

KW - TOTAL-ENERGY CALCULATIONS

KW - DISSOCIATIVE ADSORPTION

KW - SOLIDS

KW - ELECTRON-GAS

KW - GENERALIZED GRADIENT APPROXIMATION

KW - H-2 DISSOCIATION

KW - CO

KW - SINGLE-CRYSTAL SURFACES

KW - EXCHANGE-CORRELATION

UR - http://link.aps.org/doi/10.1103/PhysRevB.59.7413

U2 - 10.1103/PhysRevB.59.7413

DO - 10.1103/PhysRevB.59.7413

JO - Physical Review B Condensed Matter

JF - Physical Review B Condensed Matter

SN - 0163-1829

IS - 11

VL - 59

SP - 7413

EP - 7421

ER -