On-site energies set the reference energy for electrons associated with individual atomic orbitals. Hopping or resonance integrals occupy the connections that couple orbitals on neighboring sites. Changing either term alters the Hamiltonian matrix and therefore the calculated molecular or electronic levels. This separation lets chemists relate local atomic environments and orbital interactions to bonding patterns in molecules or solids.
When neighboring orbitals are connected by nonzero hopping or resonance integrals, their interaction changes the energy levels relative to isolated on-site values. In a molecule, this coupling provides a compact way to represent covalent bonding and conjugation. Repeated coupling across an extended structure can instead produce a set of closely related levels associated with band formation, linking local interactions to bulk electronic behavior.
The same matrix framework can describe molecular and solid-state systems, but the resulting level patterns differ with the number and arrangement of coupled sites. A molecule is represented through discrete molecular energy levels arising from its atomic orbitals and interactions. In an extended solid, many connected sites generate electronic levels associated with band formation, supporting analysis of broader electronic behavior.
A basic calculation begins by identifying the atomic orbitals used to represent the relevant sites. On-site energies are then assigned, followed by hopping or resonance integrals for neighboring orbital connections. These values form the Hamiltonian matrix, which is solved to obtain molecular or electronic energy levels. The calculated levels can then be related to structure and orbital interactions.
Chemists can apply this approach to examine covalent bonding, conjugated systems, and aromaticity without treating every electronic detail with the same level of complexity. It is also useful for extended solids, where the model connects orbital interactions with band formation and conductivity. More broadly, the calculated levels help relate molecular structure to electronic properties and reactivity.
Calculated energy levels show how the selected atomic orbitals and their couplings combine into molecular or electronic states. Comparing level patterns for different structures can reveal how changes in molecular arrangement or orbital interaction affect the electronic description. In chemistry, those relationships provide context for discussing bonding, conjugation, aromaticity, conductivity, and reactivity within the model.