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Really, this article explains well what the best times to water plants are. The ideal time to water them is in the morning before 10 am. 6 am would be good; 3 am is a bit early but also okay. The worst time to water is between 10 am and 2 pm, when the sun is hottest.
Early morning or early evening. The reason you don't want to do it in the middle of the day is for one, you will have water evaporating before it gets deep within. Two, if you live in a climate with harsh sun (i live in las vegas) the droplets can damage the leaves of the plant if it is delicate due to the sun.