I'm reading Humphreys, Reflection groups and Coxeter groups. The section "Construction of root systems" and the books uses the symbol $ \mathop {\alpha}\limits^{\sim} $ to denote an special element. But I don't know what it is. I looked for it but there is nothing about it.

I think the answer lies in section 2.9, on page 40. I quote:
"/.../ (3) There is a natural partial ordering on $V$ /.../ When $\Phi$ is irreducible, there exists a unique highest root (a long root) relative to this ordering, denoted $\tilde{a}$; it plays a crucial role in 2.11 below as well as in Chapter 4/.../"
What the asker quotes is taken from section 2.10, so it would make sense if this definition from section 2.9 carried over.