My favorite season in the franchise (anime-wise) is Railgun T and while some parts of it happen at the same time as Index Season 3 you don't need to watch that first... Actually there will be a big surprise if you watch Railgun T before Index 3 because of the retrospective foreshadowing.
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Haven't seen it yet, the only thing I know about what I haven't seen yet is there is a girl with a name that is similar to railgun who has a remote control that she bludgeons people to death with..... I think....
Yeah, Shokuhou Misaki. The other Level 5 in her School... She actually appears in the first episode of Season 2, and she's not a friend of Misaka Mikoto. She plays a big role in Season 3, and even the Manga arc that follows that.
She appears in Index second novel series: "New Testament" and she has a full arc dedicated to her there. So she's quite popular, and one of my favorite characters. (Not the top though.)