I've thought about it to help get them into the breeding mood. Sadly, the rain water here in NYC is a tad bit acidic and would probably hurt them more than it would help.
south american cichlids prefer the lower pH. never try this with african cichlids unless you've got a LOT of buffering capability. they need the hardness of minerals in their water that rain doesn't have.
An acidity of ~6 is nice. However, like the previous poster said, sometimes rain water contains a lot of contaminates. When I said "a tad bit acidic", I meant to say that the average ph of rain water in NYC is about 4.5. That's a little too low and why buffer it when you can get tap at ~6-6.5.
I live in the country so I have a well so most of the water comes from there. My angels love it. The Dempseys like it. The Blue gouramis seem to thriving in it to. Got a batch of around 200 betas out of a bucket of rain water. Maybe the rain is not that bad here.