Astronomical, Nautical, and Civil Dawn, Sunrise, Noon, Sunset, then Civil, Nautical, and Astronomical Dusk.
The spaces between the different dawns and the different Dusks are Astronomical, Nautical and Civil Twilight.
And near the bottom there's also Solar Midnight, the opposite of Noon. I'd like to see them have some sort of notation for Golden Hour and Blue Hour as well.
I'd also like to see some facility for changing the overall color. I know that blue fits with the astronomical theme, but I think it'd look great if the hue of the various blues could be changed to, say green - keeping the same saturation and brightness. Just for variety. Also the ability to set the color scheme for the complications to either matching (as it is now), or multicolor. Multicolor would distract from the theme, I know, but would make the complications more readable, which, in turn, would let me use the Solar Dial more often.
What did work is turning location services on. That kind of makes sense as only knowing the timezone isn't enough to accurately denote the multiple dawn and evening twilights. However one would think that knowing your zip code would be close enough.
Zip code works at home (or work, or wherever you entered the zip code), but starts giving increasingly inaccurate results as soon as you travel more than a few dozen miles. And without location services on, it won't know when you've traveled far enough that it should prompt you to enter your new zip code. And if you're driving across the state, do you want to keep track of every zip code you pass through?
I'd be very curious to see screenshots of someone using the Solar Dial face above the Arctic Circle, or in Antarctica, where there's days that venture far away from the nominal 12 hours of sun / 12 hours of night cycle.
I'm also curious to try taking a screenshot, say, every Monday at noon for a year, and stitch them into a time-lapse video... watch the day shrink and grow through the seasons.
FWIW, there are very well-vetted libraries, in a variety of languages, that, given longitude, latitude, and precise time and date, will calculate all the various dawn/dusk/noon/midnight times, along with the position of the sun and moon in the, and the phase of the moon.