Like you said, your spotted python is more active at night (that's when they'd normally be hunting) so it's more likely to eat at night. I generally base it on the species of snake- for instance with my Brazilian Rainbow Boas, they only like to eat in the late day early evening. Some snakes, like my Taiwan Beauty snake would eat anything, anytime- he's a hungry snake always. With the variety of snakes I've currently got, feeding 6pm or so works best. My day active snakes haven't gone to sleep yet and the night active snakes are starting to move around. Most of my snakes are dawn or dusk active so that early evening works well for them (and for the timid snakes, they get all night to eat if they need more time).
You can try it, with a dead prey item there's not much risk to the snake as long as you remove the prey item in a timely fashion if it isn't eaten. With live prey like adult mice, if the snake isn't in hunting mode, then it can become the prey item- not pretty!
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Lora