I think the best time is whenever you have time to talk calmly in private, and earlier in the day is better than later, when they are more likely to be anticipating spending the night together. Also it is better to have a few hours to let emotions settle before having a calm re-discussion later in the day so neither of you have to go to bed with things unspoken or emotions still boiling. Also avoid breaking up immediately before the person is doing something public/stressful- getting dumped minutes before making a big presentation at work is not ideal.
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