Are Ramsey numbers defined for $n=0$?

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I'm familiar with the trivial case $R(1,a)=1$, as there are no edges to colour.

Is $R(0,a)$ defined at all? Or would it similarly be trivially 0 since there are no edges and no vertices?

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It would be trivially $0$. The goal of Ramsey Theory is to study how large an ambient space (e.g., a graph) needs to be in order for prescribed substructures (e.g., subgraphs) to appear. So in that sense, it doesn't make much sense to talk about $R(0, a)$.