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The configuration that corresponds to the lowest electronic energy is called the ground state. Any other configuration is an excited state. As an example, the ground state configuration of the sodium atom is 1s 2 2s 2 2p 6 3s 1, as deduced from the Aufbau principle (see below).
Note that these electron configurations are given for neutral atoms in the gas phase, which are not the same as the electron configurations for the same atoms in chemical environments. In many cases, multiple configurations are within a small range of energies and the irregularities shown below do not necessarily have a clear relation to ...
The rule then predicts the electron configuration 1s 2 2s 2 2p 6 3s 2 3p 6 3d 9 4s 2, abbreviated [Ar] 3d 9 4s 2 where [Ar] denotes the configuration of argon, the preceding noble gas. However, the measured electron configuration of the copper atom is [Ar] 3d 10 4s 1. By filling the 3d subshell, copper can be in a lower energy state.
The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state. In quantum field theory, the ground state is usually called the vacuum state or the vacuum. If more ...
The lightest atom that requires the second rule to determine the ground state term is titanium (Ti, Z = 22) with electron configuration 1s 2 2s 2 2p 6 3s 2 3p 6 3d 2 4s 2. In this case the open shell is 3d 2 and the allowed terms include three singlets ( 1 S, 1 D, and 1 G) and two triplets ( 3 P and 3 F).
Note that these electron configurations are given for neutral atoms in the gas phase, which are not the same as the electron configurations for the same atoms in chemical environments. In many cases, multiple configurations are within a small range of energies and the small irregularities that arise in the d- and f-blocks are quite irrelevant ...
A high multiplicity state is therefore the same as a high-spin state. The lowest-energy state with maximum multiplicity usually has unpaired electrons all with parallel spin. Since the spin of each electron is 1/2, the total spin is one-half the number of unpaired electrons, and the multiplicity is the number of unpaired electrons + 1.
Each is therefore an unpaired electron, but the total spin is zero and the multiplicity is 2S + 1 = 1 despite the two unpaired electrons. The multiplicity of the second excited state is therefore not equal to the number of its unpaired electrons plus one, and the rule which is usually true for ground states is invalid for this excited state.