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It turns out that both of these atoms are more stable when the electrons "occupy" each orbital for 3d state (i.e. one electron for each of the three orbitals for chromium I think). For copper, it is more stable when the 3d state is fully occupied (i.e. two electrons for the three orbitals). Since these states happen to be more stable, the electrons are naturally arranged this way. The electrons "occupy" the 3d state at the expense of the 4s state. Therefore, instead of "occupying" the 4s state, some electrons fall out of pattern and exist in the 3d state instead. Hope this made sense.
Also, these electron configurations were experimentally determined. The explanation was that the symmetry/balance resulted in more stability, and stability should be the ground state. So technically if the electron configuration of chromium and copper didn't exist this way I suppose they wouldn't truly be in the ground state.
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