The best time to harvest mushrooms is when the veil under the caps break. That's when they're most potent. If you wait, they will get bigger, but the concentration of psilocybin/psilocin per unit mass will drop. AnswerParty!
A mushroom (or toadstool) is the fleshy, spore-bearing fruiting body of a fungus, typically produced above ground on soil or on its food source. The standard for the name "mushroom" is the cultivated white button mushroom, Agaricus bisporus; hence the word "mushroom" is most often applied to those fungi (Basidiomycota, Agaricomycetes) that have a stem (stipe), a cap (pileus), and gills (lamellae, sing. lamella) or pores on the underside of the cap.
"Mushroom" describes a variety of gilled fungi, with or without stems, and the term is used even more generally, to describe both the fleshy fruiting bodies of some Ascomycota and the woody or leathery fruiting bodies of some Basidiomycota, depending upon the context of the word. Mycotoxins
cap is convex
hymenium is adnate