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The TeXbook doesn't explain ligatures more than presenting the existing ones, the same for TeX By Topic. So, how are they defined? Is there a third way besides active characters and control sequences to ask TeX to do something unusual? Can we create new ones?

lvaneesbeeck
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    see for example http://tex.stackexchange.com/questions/106345/which-ligatures-do-the-fonts-used-in-my-document-offer/106446#106446 – David Carlisle Nov 04 '13 at 20:57

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Ligatures are defined in either the .tfm or .vf: http://tug.org/tugboat/tb11-1/tb27knut.pdf

or in the font itself if using a non-TeX (.tfm or .vf) font using a TeX-variant such as XeTeX or LuaTeX.

WillAdams
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