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Atoms always want to be in the lowest energy state possible. Thus it requires less energy for an atom to have electrons in a 4s orbital rather than a 3d orbital. This can get confusing bc 4 is considered a higher energy level.
When we look at the order of elements in the periodic table, we notice that the first two elements in the fourth row are part of the s-block. Therefore, 4s has a lower energy than 3d. However, for multi electron atoms after atomic number 20, 4s has a higher energy than 3d.
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