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The relationship between SKOS and Topic Maps is relatively straightforward: SKOS is an RDF vocabulary for representing thesauri, while Topic Maps is an ontology technology that is more-or-less equivalent to RDF itself.
You can use SKOS as a Topic Maps vocabulary if you want (as described here
http://www.garshol.priv.no/blog/10.html).
In the bigger picture of things, SKOS lets you represent thesauri, but Topic Maps let you go a lot further. For more detail, see
http://www.ontopia.net/topicmaps/materials/tm-vs-thesauri.html
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