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Thursday. Trust me, being self-employed I've done a lot of experimenting.
The ideal 3-day workweek is easy: that's MWT — Monday, Wednesday, Thursday. It makes Monday easier, because you know you have the next day off. You arrive Wednesday feeling like it's Monday, except tomorrow is Thursday, which is Friday for you! Then, every week, you get a three day weekend to cap it off! It's ideal, and I recommend the MWT work schedule for everybody.
Working a 4-day workweek, especially 4 10-hour days, is more complicated. The entire dynamic changes. The ideal 4-day workweek is MTWF.
You have to think in terms of psychology: three 10 hour workdays in a row is easy to handle, it just feels like a heavy-duty, but abbreviated, 3-day workweek. Thursday feels like a taste of early weekend, which puts you in a good mood. And then Friday is a cakewalk because it's only one day. Then you start your weekend refreshed, because you're only coming off a single day of work since your last break, you're not recuperating from 2 or more 10 hour days.
What you want to avoid is ever being in a position where you find yourself thinking "Christ, 2 more days of this" — EXCEPT on Mondays, when that's ok for several reasons: you're still refreshed from the weekend, plus on Monday, you're really used to thinking "Christ, 4 more days in a row of this", so on Monday nights, only 2 more days seems like a relief, not a burden.
Whatever you do, don't take Monday off. Mondays are never relaxing, whether you're working or not, so you might as well work. It doesn't even count as a 3-day weekend if the extra day is Monday. Your body will never let you feel like Monday is a weekend day.