A quantum chemical mechanism for the water-initiated decomposition of silica

Janet E. Del Bene; Keith Runge; Rodney J. Bartlett

doi:10.1016/S0927-0256(02)00432-9

A quantum chemical mechanism for the water-initiated decomposition of silica

Janet E. Del Bene, Keith Runge, Rodney J. Bartlett

Materials Science and Engineering

Research output: Contribution to journal › Conference article › peer-review

24 Scopus citations

Abstract

An ab initio quantum chemical investigation of the interaction of water with amorphous silica is carried out using model systems that contain the Si-O-Si bridging unit. Interaction of the silicon-oxygen bond with a water dimer is found to be most favorable, in contrast to the Michalske-Freiman model, which assumes that the interaction occurs with a single water molecule. Formation of a five-coordinated silicon atom is an essential intermediate in the bond fracture process, which involves proton transfer from the water dimer to the bridging oxygen, proton transfer within the water dimer, and the formation of a new Si-O bond. The activation barrier to rupture the Si-O bond in the Si-O-Si unit in the presence of water dimer is ∼30 kcal/mol.

Original language	English (US)
Pages (from-to)	102-108
Number of pages	7
Journal	Computational Materials Science
Volume	27
Issue number	1-2
DOIs	https://doi.org/10.1016/S0927-0256(02)00432-9
State	Published - Mar 2003
Event	E-MRS 2002, Symposium A - Strasbourg, France Duration: Jun 18 2002 → Jun 21 2002

Keywords

Ab initio quantum chemistry
Hydrolytic weakening
Quantum mechanics
Silica
Water
Water dimer

ASJC Scopus subject areas

General Computer Science
General Chemistry
General Materials Science
Mechanics of Materials
General Physics and Astronomy
Computational Mathematics

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10.1016/S0927-0256(02)00432-9

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title = "A quantum chemical mechanism for the water-initiated decomposition of silica",

abstract = "An ab initio quantum chemical investigation of the interaction of water with amorphous silica is carried out using model systems that contain the Si-O-Si bridging unit. Interaction of the silicon-oxygen bond with a water dimer is found to be most favorable, in contrast to the Michalske-Freiman model, which assumes that the interaction occurs with a single water molecule. Formation of a five-coordinated silicon atom is an essential intermediate in the bond fracture process, which involves proton transfer from the water dimer to the bridging oxygen, proton transfer within the water dimer, and the formation of a new Si-O bond. The activation barrier to rupture the Si-O bond in the Si-O-Si unit in the presence of water dimer is ∼30 kcal/mol.",

keywords = "Ab initio quantum chemistry, Hydrolytic weakening, Quantum mechanics, Silica, Water, Water dimer",

author = "{Del Bene}, {Janet E.} and Keith Runge and Bartlett, {Rodney J.}",

note = "Funding Information: This work is support by NSF Grant no. DMR 9980015.; E-MRS 2002, Symposium A ; Conference date: 18-06-2002 Through 21-06-2002",

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TY - JOUR

T1 - A quantum chemical mechanism for the water-initiated decomposition of silica

AU - Del Bene, Janet E.

AU - Runge, Keith

AU - Bartlett, Rodney J.

N1 - Funding Information: This work is support by NSF Grant no. DMR 9980015.

PY - 2003/3

Y1 - 2003/3

N2 - An ab initio quantum chemical investigation of the interaction of water with amorphous silica is carried out using model systems that contain the Si-O-Si bridging unit. Interaction of the silicon-oxygen bond with a water dimer is found to be most favorable, in contrast to the Michalske-Freiman model, which assumes that the interaction occurs with a single water molecule. Formation of a five-coordinated silicon atom is an essential intermediate in the bond fracture process, which involves proton transfer from the water dimer to the bridging oxygen, proton transfer within the water dimer, and the formation of a new Si-O bond. The activation barrier to rupture the Si-O bond in the Si-O-Si unit in the presence of water dimer is ∼30 kcal/mol.

AB - An ab initio quantum chemical investigation of the interaction of water with amorphous silica is carried out using model systems that contain the Si-O-Si bridging unit. Interaction of the silicon-oxygen bond with a water dimer is found to be most favorable, in contrast to the Michalske-Freiman model, which assumes that the interaction occurs with a single water molecule. Formation of a five-coordinated silicon atom is an essential intermediate in the bond fracture process, which involves proton transfer from the water dimer to the bridging oxygen, proton transfer within the water dimer, and the formation of a new Si-O bond. The activation barrier to rupture the Si-O bond in the Si-O-Si unit in the presence of water dimer is ∼30 kcal/mol.

KW - Ab initio quantum chemistry

KW - Hydrolytic weakening

KW - Quantum mechanics

KW - Silica

KW - Water

KW - Water dimer

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U2 - 10.1016/S0927-0256(02)00432-9

DO - 10.1016/S0927-0256(02)00432-9

M3 - Conference article

SN - 0927-0256

VL - 27

SP - 102

EP - 108

JO - Computational Materials Science

JF - Computational Materials Science

IS - 1-2

T2 - E-MRS 2002, Symposium A

Y2 - 18 June 2002 through 21 June 2002

ER -

A quantum chemical mechanism for the water-initiated decomposition of silica

Abstract

Keywords

ASJC Scopus subject areas

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