A pseudopotential hole-particle formalism is developed for the treatment of rare-gas excimers and excited rare-gas clusters. The formalism relies on the definition of a model Hamiltonian on the basis of single hole-particle excitations (from the neutral closed shell ground state) involving localized np hole orbitals and any orthogonal molecular orbital (MO) basis set for the excited particle. Hole contributions in the Hamiltonian matrix elements are taken into account via distance- and orientation-dependent transfer integrals (hole delocalization) and repulsion integrals like in diatomic in molecules treatments of rare gas ions, while the contribution of the excited particle is included through an explicit quantal treatment via one-electron e-Rg and averaged e-Rg(+) pseudopotentials. Core-polarization pseudopotentials are also added to account for core-polarization and core-Rydberg correlation effects. Some approximated core-Rydberg two-electron integrals needed for adequate space and spin multiplicity of the excited states are also included. The possible applications and extensions of this formalism are discussed.