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So reading through the psychic portion of the rulebook, I can't determine when we cast psychic abilities, asides from the obvious ones (shooting attacks in the shooting phase). I know for Eldar specific psychic abilities, the non-shooting ones must be done in the beginning of the phase. What about the general ones? Do I have to cast them in beginning of the turn, or when an event happens and I need it there and then (i.e.: changing Overwatch BS 1 to normal BS skill)?

Page 68 for any of the BRB psychic powers.

Your codex for anything else.