Hi Brian, you'll be arriving in prime schoolie striper time. That would be my number 1 target but it depends on tides and time of day. I am sure some other replies can give you a few spots to try but generally you want outgoing tide coinciding with low light periods. To make things more complicated we've had a lot of muddy water and flooding in the Potomac this year which isn't ideal for fly fishing, but it could very well clear up in the next few weeks.
If you do a quick Google search for "USGS Potomac Little Falls" you should find the USGS flow gage on the Potomac located a few miles upriver from DC. If the flow is around 15,000 CFS or less you should find good fishing around Chain Bridge or upstream in the rapids of Little Falls. Wide variety of fish up there but most everything will eat clousers. Along with the schoolies you have a reasonable chance at smallmouth bass, walleye, and catfish. This area is dangerously deep and fast and wading is 100% impossible so you still won't need waders.
I agree with other comments about trout - however if you are able to leave between 1-2 pm time frame you can probably reach some good stocked water in MD. Check the MDNR website for stocking schedules - I am not super familiar with fall stockings but I do know some of the stocked waters are pretty nice for how close they are - Patapsco River and Little Patuxent are pretty neat.
IMO Shenandoah National Park deserves a day trip. You won't want to leave once you are there, and it gets dark early in October.
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http://www.tpfr.org
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