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I'm going to have to third or fourth the West Wing - Two Cathedrals episode as the best ever. I actually downloaded that episode just to watch on occasion. It has in my opinion one of the best scenes ever as well when the President locks himself in the cathedral and goes on the tirade questioning god. Reguardless of your religious affiliation, it is a beautifully written, acted, and shot scene. Especially if you were at least a semi-fan of the show and had some emotional investment in the characters.
This reminded me of another West Wing episode earlier that season that in my opinion is almost as good. I think it was called 17 People, something similar to that at least. It was the one where Toby discovered Jed's secret, and all the interactions in that episode are very well written and acted as well. The tensions just under the surface are great, along with Toby bouncing the ball off his walls as he pieces it together.
Also up for grabs, there was an episode of the X-Files called Bad Blood I think. It showed the story from both Mulder and Skully's perspectives and is hilarious how it plays off of the inside jokes from the series.
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...And then I found $5!
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