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Theoretical calculations of [AlO4/M+]0 defects in quartz and crystal-chemical controls on the uptake of Al

Published online by Cambridge University Press:  05 July 2018

S. M. Botis  and
Yuanming Pan
S. M. Botis*
Affiliation:
Department of Geological Sciences, University of Saskatchewan, Saskatoon SK S7N 5E2, Canada
Yuanming Pan
Affiliation:
Department of Geological Sciences, University of Saskatchewan, Saskatoon SK S7N 5E2, Canada
*
* E-mail: [email protected]
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Abstract

The [AlO4/M+]0 (where M = H, Li, Na and K) defects in α-quartz have been investigated by ab initio calculations at the density functional theory (DFT) level, using the CRYSTAL06 code, 72-atom supercells, and all-electron basis sets. Our DFT calculations yielded substantially improved results than previous cluster calculations with minimal basis sets. For example, the [AlO4/M+(a<)]0 defects with M = H, Li and Na have been shown to be more stable than their [AlO4/M+(a>)]0 structural analogues (where a> and a< denote the location of the charge-compensating ion on the long-bond and short-bond side respectively), correctly predicting the common occurrence of paramagnetic [AlO4/M+(a>)]+ centres. In addition, the [AlO4/K+]0 defects have been investigated for the first time and are shown to be stable in quartz. Moreover, our calculations confirm previous suggestions that incorporation of the [AlO4/M+]0 defects results in significant structural relaxations that extend at least to the nearest Si atoms and give Li—O and Na—O bond distances in better agreement with the experimentally obtained values. The present theoretical results on the [AlO4/M+]0 defects provide a more complete picture for the coupled Al3+—M+ substitutions and hence new insights into crystal-chemical controls on the uptake of Al in quartz.

Keywords

ab initio calculationsDFTquartzAlHLiNaK.
Type
Research Article
Information
Mineralogical Magazine , Volume 73 , Issue 4 , August 2009 , pp. 537 - 550
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2009

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