Welcome to the Psionicist guide!
The Psionicist is one of the classes that has seen the light at the end of the tunnel the fewest. With the constant nerfs and ever so slightly buffs, it's a class that's been pushed into the ground very often.
The last time the Psionicist was ever considered was meta was back in 9.1, right after Demonologist got introduced to the game.
In 14.0 however, it finally gains more standing ground and can be a competing class among its peers.
The Psi focusses on getting into enemies' minds and completely brizzling it to mush with Mental Impact abilities.
It has an enormous AOE burst that very few classes can top to.
The Psi has quite some defensives but despite all that, remains along with Mage one of the 2 classes that serve no other purpose in the game than just being a DPS, and thus has a much smaller toolkit than other classes.
The PvE DPS build
In PvE DPS, the Psionicist focusses on applying it's Blade Storm followed by Agony. The order is important because of the ruby Annihilation. It then rotates between Astral Venom and Scorching because of the rubies Breakdown and Pyrolysis.
Breakdown relies on your DOT's and Phantoms, so give priority to applying the 2 DOT's, followed by keeping up 6 phantoms at all times.
Once that's covered, focus on the Vertex and Decomposition cooldowns. Try doing it every 15s: Vertex, wait for Phantoms to stack on the target, Decomposition, followed by Meditation to help you get those 6 Phantoms back up asap, because Meditation gives Brain Fragments from its ruby.
And repeat from there.
It's a very fast paced gameplay so it might take some getting used to.
You'll notice Scorching greyed out when your stress gets too high, because it requires stress to be below 100. If that's the case, you want to use Psychosis. If that's on cooldown, spam a few more Astral Venoms as that doesn't need stress.