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Because the 4d electrons experience a lower effective charge from the nucleus at this point than the 5s electrons. Long story is that it has to do with the energy lost from spin-pairing. That means that it takes more energy to spin-pair the 5s electron than the energy difference between the 4d and 5s orbitals, so it will push the electron up to the 4d orbital since it requires slightly less energy. At the periods containing cromium and copper, this is where that effect takes place. You can demonstrate this to yourself by calculating the Z(eff) for the electrons using Slater's Rule, and you will see the change in Z(eff) for yourself.

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Q: Why does an electron occupy the 4s orbitals before the 3rd orbital?
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