Intruder State

In quantum and theoretical chemistry, an intruder state is a particular situation arising in perturbative evaluations, where the energy of the perturbers is comparable in magnitude to the energy associated to the zero order wavefunction. In this case, a divergent behavior occurs, due to the nearly zero denominator in the expression of the perturbative correction.

Multi-rerefence wavefunction methods are not immune. There are ways to identity them. The natural orbitals of the perturbation expansion are a useful diagnostic for detecting intruder state effects. Sometimes what appears to be an intruder state is simply a change in basis.

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    To educate the wise man, the State exists; and with the appearance of the wise man, the State expires. The appearance of character makes the state unnecessary. The wise man is the State.
    Ralph Waldo Emerson (1803–1882)