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Avoided crossing


In quantum physics and quantum chemistry, an avoided crossing (sometimes called intended crossing,non-crossing or anticrossing) is the phenomenon where two eigenvalues of an Hermitian matrix representing a quantum observable and depending on N continuous real parameters cannot become equal in value ("cross") except on a manifold of N-2 dimensions. In the case of a diatomic molecule (with one parameter, namely the bond length), this means that the eigenvalues cannot cross at all. In the case of a triatomic molecule, this means that the eigenvalues can coincide only at a single point (see conical intersection).

This is particularly important in quantum chemistry. In the Born–Oppenheimer approximation, the electronic molecular Hamiltonian is diagonalized on a set of distinct molecular geometries (the obtained eigenvalues are the values of the adiabatic potential energy surfaces). The geometries for which the potential energy surfaces are avoiding to cross are the locus where the Born–Oppenheimer approximation fails.

Study of a two-level system is of vital importance in quantum mechanics because it embodies simplification of many of physically realizable systems. The effect of perturbation on a two-state system Hamiltonian is manifested through avoided crossings in the plot of individual energy vs energy difference curve of the eigenstates. The two-state Hamiltonian can be written as


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