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Oxygen is found in 3 forms: nascent (O), molecular (O2, the most common) and ozone (O3). Nascent oxygen, due to its electronic configuration (i.e how many electrons it has and how they're spread out across its electronic shells) is unstable, and tends to quickly form bonds with another O, forming O2. This is also the case e.g. for hydrogen, which is usually found as H2.
You can find O in this form in some environments, in the upper atmosphere there is enough UV radiation to break up O2 into O.
Can you breathe just O by itself without it being in O~2~ molecule?
Edit: I did some searching and apparantly you couldn't breathe just an Oxygen atom by itself, it needs to be an O~2~. (Correct me if I'm wrong)
I suspect it would rapidly react and give off energy as heat. This would likely be incompatible with life.
Not an expert.