Symmetry-adapted linear combination (${\Phi }_{\Gamma }={\sum }_i{c}_i{\varphi }_i$)

A linear combination of atomic orbitals chosen to transform under an irreducible representation of the molecular point group. Relative orbital signs must be transformed as well as the positions of their centres. Such combinations organize a Hamiltonian operator into symmetry blocks; combinations of the same symmetry generally still mix and need not themselves be molecular orbitals.

Four equivalent $s$ atomic orbitals at the vertices of a regular tetrahedron carry the tetrahedral symmetry representation $A_1\oplus T_2$. The normalized equal sum is $A_1$; three coordinate-sign combinations span $T_2$. Every normalized coefficient vector has entries $\pm 1/2$ in a suitable orthonormal real basis. These functions simplify a Hamiltonian invariant under the tetrahedral operations, but equivalent symmetry copies on other sites may still mix.