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Quantum numbers describe values of conserved quantities in the dynamics of the quantum system. Perhaps the most peculiar aspect of quantum mechanics is the quantization of observable quantities. This is distinguished from classical mechanics where the values can range continuously. They often describe specifically the energies of electrons in atoms, but other possibilities include angular momentum, spin etc. Since any quantum system can have one or more quantum numbers, it is a rigorous job to list all possible quantum numbers.
Results from spectroscopy indicated that up to two electrons can occupy a single orbital. However two electrons can never have the same exact quantum state nor the same set of quantum numbers according to Hund's Rules, which addresses the Pauli exclusion principle. A fourth quantum number with two possible values was added as an ad hoc assumption to resolve the conflict; this supposition could later be explained in detail by relativistic quantum mechanics and from the results of the renowned Stern-Gerlach experiment.
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