Ab initio investigation of dissolution mechanisms in aluminosilicate minerals

Christin P. Morrow, Shikha Nangia, Barbara Jane Garrison

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The reactions of aluminosilicate clusters with water are investigated using ab initio calculations. There are several reaction sites on a mineral surface, and, in the case of aluminosilicates, the dissolution chemistry is dictated by chemically distinct surface termination sites: Al and Si. Environmental factors such as pH determine the protonation state and configuration around these terminal sites. The dissolution mechanisms for Al- and Si-terminated sites in protonated, neutral, and deprotonated states are determined using density functional theory calculations. In all protonation states, Si are tetra-coordinated; however, the ability of Al to exist in tetra-, penta-, and hexa-coordination states makes the dissolution mechanisms for the two types of terminal sites fundamentally different. The calculated barrier heights for Al-terminated sites are predicted to be lower than those for Si-terminated sites, a trend that has been observed in experimental studies. The sensitivity of the calculations on the choice of density functionals and basis sets is tested using three functionals: B3LYP, PBE1PBE, and M05-2X, in combination with the 6-311+G(d,p) and MG3S basis sets. For all these calculations, the geometries of the stationary points along the reaction path and the barrier heights are presented.

Original languageEnglish (US)
Pages (from-to)1343-1352
Number of pages10
JournalJournal of Physical Chemistry A
Volume113
Issue number7
DOIs
StatePublished - Feb 19 2009

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Minerals
dissolving
Dissolution
minerals
Protonation
functionals
Density functional theory
chemistry
density functional theory
trends
Geometry
aluminosilicate
Water
sensitivity
geometry
configurations
water

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

Morrow, Christin P. ; Nangia, Shikha ; Garrison, Barbara Jane. / Ab initio investigation of dissolution mechanisms in aluminosilicate minerals. In: Journal of Physical Chemistry A. 2009 ; Vol. 113, No. 7. pp. 1343-1352.
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Ab initio investigation of dissolution mechanisms in aluminosilicate minerals. / Morrow, Christin P.; Nangia, Shikha; Garrison, Barbara Jane.

In: Journal of Physical Chemistry A, Vol. 113, No. 7, 19.02.2009, p. 1343-1352.

Research output: Contribution to journalArticle

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