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Because electrons are identical to (i.e., indistinguishable from) each other, the wave function of an atom with more than one electron must satisfy special conditions. The problem of identical particles does not arise in classical physics, where the objects are large-scale and can always be distinguished, at least in principle. There is no way, however, to differentiate two electrons in the same atom, and the form of the wave function must reflect this fact. The overall wave function Ψ of a system of identical particles depends on the coordinates of all the particles. If the coordinates of two of the particles are interchanged, the wave function must remain unaltered or, at most, undergo a change of sign; the change of sign is permitted because it is Ψ^{2} that occurs in the physical interpretation of the wave function. If the sign of Ψ remains unchanged, the wave function is said to be symmetric with respect to interchange; if the sign changes, the function is antisymmetric.

The symmetry of the wave function for identical particles is closely related to the spin of the particles. In quantum field theory (see below Quantum electrodynamics), it can be shown that particles with half-integral spin (1/2, 3/2, etc.) have antisymmetric wave functions. They are called fermions after the Italian-born physicist Enrico Fermi. Examples of fermions are electrons, protons, and neutrons, all of which have spin 1/2. Particles with zero or integral spin (e.g., mesons, photons) have symmetric wave functions and are called bosons after the Indian mathematician and physicist Satyendra Nath Bose, who first applied the ideas of symmetry to photons in 1924–25.

The requirement of antisymmetric wave functions for fermions leads to a fundamental result, known as the exclusion principle, first proposed in 1925 by the Austrian physicist Wolfgang Pauli. The exclusion principle states that two fermions in the same system cannot be in the same quantum state. If they were, interchanging the two sets of coordinates would not change the wave function at all, which contradicts the result that the wave function must change sign. Thus, two electrons in the same atom cannot have an identical set of values for the four quantum numbers n, l, m, m_{s}. The exclusion principle forms the basis of many properties of matter, including the periodic classification of the elements, the nature of chemical bonds, and the behaviour of electrons in solids; the last determines in turn whether a solid is a metal, an insulator, or a semiconductor (see atom; matter).

The Schrödinger equation cannot be solved precisely for atoms with more than one electron. The principles of the calculation are well understood, but the problems are complicated by the number of particles and the variety of forces involved. The forces include the electrostatic forces between the nucleus and the electrons and between the electrons themselves, as well as weaker magnetic forces arising from the spin and orbital motions of the electrons. Despite these difficulties, approximation methods introduced by the English physicist Douglas R. Hartree, the Russian physicist Vladimir Fock, and others in the 1920s and 1930s have achieved considerable success. Such schemes start by assuming that each electron moves independently in an average electric field because of the nucleus and the other electrons; i.e., correlations between the positions of the electrons are ignored. Each electron has its own wave function, called an orbital. The overall wave function for all the electrons in the atom satisfies the exclusion principle. Corrections to the calculated energies are then made, which depend on the strengths of the electron-electron correlations and the magnetic forces.

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