Come on, is this even a question? A million times yes.
Even if you already have bride and groom photos scheduled for earlier in the day, add in a sunset session into your timeline. It is the best lighting of the day.
Head to Google and look up your date and location's sunset time. Plan 20-30 minutes before the sunset time it shows. This gives you "golden hour" photos and sunset!
When creating your timeline, try to make this around the time your guests are eating dinner. Ideally, you have already had your food but your guests are still eating. They won't even notice you stepped away!