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Energetics of substituted polyhedral oligomeric silsesquioxanes: a DFT study

Published online by Cambridge University Press:  30 July 2015

Abu Asaduzzaman ,
Keith Runge ,
Krishna Muralidharan ,
P.A. Deymier  and
Lianyang Zhang
Abu Asaduzzaman*
Affiliation:
Materials Science and Engineering, University of Arizona, Tucson, AZ 85721, USA
Keith Runge
Affiliation:
Materials Science and Engineering, University of Arizona, Tucson, AZ 85721, USA Quantum Theory Project, University of Florida, Gainesville, FL 32611, USA
Krishna Muralidharan
Affiliation:
Materials Science and Engineering, University of Arizona, Tucson, AZ 85721, USA
P.A. Deymier
Affiliation:
Materials Science and Engineering, University of Arizona, Tucson, AZ 85721, USA
Lianyang Zhang
Affiliation:
Civil Engineering and Engineering Mechanics, University of Arizona, Tucson, AZ 85721, USA
*
Address all correspondence to Abu Asaduzzaman at[email protected]
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Abstract

First principles density functional theory calculations were conducted to investigate the structures and energetics of polyhedral oligomeric silsesquioxane (POSS) molecules with varying aluminum and alkali (sodium or potassium) concentrations. Notable trends emerge from this study namely, (1) the thermodynamic stability of the substituted POSS molecules is critically dependent on the interplay between size and composition of the POSS structures, and (2) larger POSS structures provide lower central electron density and hence better accommodate the central alkali atom. These observations, when viewed in the context of aluminosilicate based geopolymers, provide fundamental insights into the relations that describe the structure composition interplay of their underlying monomers.

Type
Research Letters
Information
MRS Communications , Volume 5 , Issue 3 , September 2015 , pp. 519 - 524
Copyright
Copyright © Materials Research Society 2015 

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