It really depends on what area you live in whether rainwater is suitable for your tank (or human consumption for that matter...)
Large metropolitan areas, or areas with a lot of traffic flow, I would advise against it, but someone who lives way out in the backcountry could certainly use rainwater without any problems. Best way to know if it's acid rain is to test the ph... it's acidic after all. If you get a really peculiar reading, don't use it.
My grandmother still collects rain in a barrel to water her houseplants and wash her dishes with to this very day.
I would suggest in any event that you let rainwater age in the barrel for a few days, just to make sure any harmful stuff in the cloud has a chance to settle and/or gas off, depending upon the impurities present in your little neck of the woods, and filtration through a carbon filter before introduction to your tank, just to be sure, but then, I'm really anal about water quality.
I think there's a couple topics on wetman's site (can't remember the link name, sorry), regarding using rainwater.