It's not possible with spells that are always available, like Exorcism, but it can be done easily with abilities that should be cast on every possible cooldown and have a proc that may reset that cooldown or make it instant cast, for example Starsurge, Mangle (Bear), Pyroblast!, Deep Freeze, etc. You can just use a 2-step dps macro to always be spamming that button along with your main rotation.
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