TY - JOUR

T1 - Chemisorption with overcompleteness, nonorthogonality, and electron correlation

T2 - II. Large U limit

AU - Bagchi, Amitabha

AU - Cohen, Morrel H.

PY - 1976

Y1 - 1976

N2 - The pseudo-Green's-function theory of hydrogen chemisorption, developed in a previous paper, is extended to treat the situation when the intra-atomic Coulomb repulsion on the adatom is very large, so that hydrogen chemisorbs in a magnetic configuration. The theory takes systematically into account the overcompleteness and nonorthogonality of wave functions describing the problem, and electron-electron interaction. The metaladsorbate system is described in terms of an overcomplete basis set consisting of the eigenstates (both occupied and unoccupied) of the metal and the occupied electronic state on the adatom. The overcompleteness problem is satisfactorily dealt with through the introduction of the pseudo Green's functions, and their equations of motion are worked out in detail. In the limit of a large intra-atomic Coulomb repulsion U, there is an electronic spin localized on the adsorbed hydrogen atom. This is shown by rearranging the equations of motion of the pseudo Green's function in that case, so that they manifestly describe the scattering of metal electrons off of the localized spin. The physics of hydrogen chemisorption in this limit is discussed, and comparison is made with previous theoretical work.

AB - The pseudo-Green's-function theory of hydrogen chemisorption, developed in a previous paper, is extended to treat the situation when the intra-atomic Coulomb repulsion on the adatom is very large, so that hydrogen chemisorbs in a magnetic configuration. The theory takes systematically into account the overcompleteness and nonorthogonality of wave functions describing the problem, and electron-electron interaction. The metaladsorbate system is described in terms of an overcomplete basis set consisting of the eigenstates (both occupied and unoccupied) of the metal and the occupied electronic state on the adatom. The overcompleteness problem is satisfactorily dealt with through the introduction of the pseudo Green's functions, and their equations of motion are worked out in detail. In the limit of a large intra-atomic Coulomb repulsion U, there is an electronic spin localized on the adsorbed hydrogen atom. This is shown by rearranging the equations of motion of the pseudo Green's function in that case, so that they manifestly describe the scattering of metal electrons off of the localized spin. The physics of hydrogen chemisorption in this limit is discussed, and comparison is made with previous theoretical work.

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U2 - 10.1103/PhysRevB.13.5351

DO - 10.1103/PhysRevB.13.5351

M3 - Article

AN - SCOPUS:27544449310

VL - 13

SP - 5351

EP - 5361

JO - Physical Review B

JF - Physical Review B

SN - 0163-1829

IS - 12

ER -