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In period 4, Chromium and Copper fill their shells differently than you'd expect. Instead of Chromium having the electron configuration [Ar] 3d4 4s2, it's actually more stable with the following configuration [Ar] 3d5 4s1. Likewise, Copper is expected to be [Ar] 3d9 4s2 but it fills the d shell and becomes [Ar] 3d10 4s1. This pattern also occurs in period 5.
For chromium and copper, a completely full or half full d-sublevel is more stable than a partially filled d sub-level, so an electron from the 4s orbital is excited and rises to the 3d orbital.
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