Avoided crossing (sometimes misleadingly called intended crossing). The eigenvalues of a Hermitian matrix depending on N continuous real parameters cannot cross except at a manifold of N-2 dimensions. In the case of a diatomic molecule (one parameter, which describes the bond length), this means that the eigenvalues do not cross. In the case of a triatomic molecule, this means that the eigenvalues can intersect at a point only (see conical intersection).
This is particularly important in quantum chemistry. In the Born-Oppenheimer approach, 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.
A CASE STUDY OF STATE-SPECIFIC AND STATE-AVERAGED BRUECKNER EQUATION-OF-MOTION COUPLED-CLUSTER THEORY: THE IONIC-COVALENT AVOIDED CROSSING IN LITHIUM FLUORIDE
Aug 01, 2005; State-specific Brueckner equation-of-motion coupled-cluster theory (SS-B-EOMCC) is summarized, which can be considered an...