Theoretical study on molecular and dissociative chemisorptions of an O2 molecule on an Ag surface

dipped adcluster model combined with symmetry-adapted cluster-configuration interaction method

Hiroshi Nakatsuji, Hiromi Nakai

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

Chemisorption of an oxygen molecule on a silver surface is studied theoretically with the use of the dipped adcluster model (DAM) for AgxO2 with x=2 and 4. Electron correlation in low-lying surface states and electron transfer from bulk metal are described by combining DAM with the symmetry-adapted cluster (SAC) CI method. For chemisorption, electron transfer from the bulk metal to the adcluster and the electrostatic image force are important. They cannot be treated by the conventional cluster model, but are dealt with by the DAM. Three low-lying states, 2A1, 2A2, and 2B1, of the adclusters Ag2O- 2 and Ag4O- 2 are involved in the chemisorption. In the molecular adsorption state, the 2A1 state is assigned to peroxide (O2- 2) species and the 2A2 and 2B1 states to superoxide (O- 2) species. The OO stretching frequencies are in agreement with the experimental values. In the potential energy curves of Ag4O- 2, another potential minimum corresponding to the dissociative adsorption state is obtained for the 2A1 state. The energetics of the molecular and dissociative adsorptions show reasonable agreement with experiments.

Original languageEnglish
Pages (from-to)283-286
Number of pages4
JournalChemical Physics Letters
Volume174
Issue number3-4
DOIs
Publication statusPublished - 1990 Nov 9
Externally publishedYes

Fingerprint

Chemisorption
chemisorption
configuration interaction
Molecules
symmetry
Adsorption
adsorption
molecules
electron transfer
Metals
Electron correlations
Electrons
inorganic peroxides
Peroxides
Surface states
peroxides
Potential energy
Silver
Superoxides
metals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

@article{4bbd8c2924cc4b57840a10b83d5bbb80,
title = "Theoretical study on molecular and dissociative chemisorptions of an O2 molecule on an Ag surface: dipped adcluster model combined with symmetry-adapted cluster-configuration interaction method",
abstract = "Chemisorption of an oxygen molecule on a silver surface is studied theoretically with the use of the dipped adcluster model (DAM) for AgxO2 with x=2 and 4. Electron correlation in low-lying surface states and electron transfer from bulk metal are described by combining DAM with the symmetry-adapted cluster (SAC) CI method. For chemisorption, electron transfer from the bulk metal to the adcluster and the electrostatic image force are important. They cannot be treated by the conventional cluster model, but are dealt with by the DAM. Three low-lying states, 2A1, 2A2, and 2B1, of the adclusters Ag2O- 2 and Ag4O- 2 are involved in the chemisorption. In the molecular adsorption state, the 2A1 state is assigned to peroxide (O2- 2) species and the 2A2 and 2B1 states to superoxide (O- 2) species. The OO stretching frequencies are in agreement with the experimental values. In the potential energy curves of Ag4O- 2, another potential minimum corresponding to the dissociative adsorption state is obtained for the 2A1 state. The energetics of the molecular and dissociative adsorptions show reasonable agreement with experiments.",
author = "Hiroshi Nakatsuji and Hiromi Nakai",
year = "1990",
month = "11",
day = "9",
doi = "10.1016/0009-2614(90)85346-E",
language = "English",
volume = "174",
pages = "283--286",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "3-4",

}

TY - JOUR

T1 - Theoretical study on molecular and dissociative chemisorptions of an O2 molecule on an Ag surface

T2 - dipped adcluster model combined with symmetry-adapted cluster-configuration interaction method

AU - Nakatsuji, Hiroshi

AU - Nakai, Hiromi

PY - 1990/11/9

Y1 - 1990/11/9

N2 - Chemisorption of an oxygen molecule on a silver surface is studied theoretically with the use of the dipped adcluster model (DAM) for AgxO2 with x=2 and 4. Electron correlation in low-lying surface states and electron transfer from bulk metal are described by combining DAM with the symmetry-adapted cluster (SAC) CI method. For chemisorption, electron transfer from the bulk metal to the adcluster and the electrostatic image force are important. They cannot be treated by the conventional cluster model, but are dealt with by the DAM. Three low-lying states, 2A1, 2A2, and 2B1, of the adclusters Ag2O- 2 and Ag4O- 2 are involved in the chemisorption. In the molecular adsorption state, the 2A1 state is assigned to peroxide (O2- 2) species and the 2A2 and 2B1 states to superoxide (O- 2) species. The OO stretching frequencies are in agreement with the experimental values. In the potential energy curves of Ag4O- 2, another potential minimum corresponding to the dissociative adsorption state is obtained for the 2A1 state. The energetics of the molecular and dissociative adsorptions show reasonable agreement with experiments.

AB - Chemisorption of an oxygen molecule on a silver surface is studied theoretically with the use of the dipped adcluster model (DAM) for AgxO2 with x=2 and 4. Electron correlation in low-lying surface states and electron transfer from bulk metal are described by combining DAM with the symmetry-adapted cluster (SAC) CI method. For chemisorption, electron transfer from the bulk metal to the adcluster and the electrostatic image force are important. They cannot be treated by the conventional cluster model, but are dealt with by the DAM. Three low-lying states, 2A1, 2A2, and 2B1, of the adclusters Ag2O- 2 and Ag4O- 2 are involved in the chemisorption. In the molecular adsorption state, the 2A1 state is assigned to peroxide (O2- 2) species and the 2A2 and 2B1 states to superoxide (O- 2) species. The OO stretching frequencies are in agreement with the experimental values. In the potential energy curves of Ag4O- 2, another potential minimum corresponding to the dissociative adsorption state is obtained for the 2A1 state. The energetics of the molecular and dissociative adsorptions show reasonable agreement with experiments.

UR - http://www.scopus.com/inward/record.url?scp=0000068089&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000068089&partnerID=8YFLogxK

U2 - 10.1016/0009-2614(90)85346-E

DO - 10.1016/0009-2614(90)85346-E

M3 - Article

VL - 174

SP - 283

EP - 286

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 3-4

ER -