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It is rather difficult to answer this question without some sort of context. However, in general terms, I would say that an electron will always occupy the lowest possible energy state. If one is considering a single atom, then an electron will always occupy the lowest energy orbital (for a full list of orbital energies see the Wikipedia article "electronic configuration"). However, if other atoms are present then the electron will not necessarily occupy the lowest energy orbital. For example, in the formation of sulfur hexafluoride electrons are promoted from the 3s and 3p sub shells to the 3d sub shell, whilst this does require energy, the energy released in bonding with fluorine more than compensates for this.

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