A pseudopotential study of molecular spectroscopy in rare gas matrices: absorption of NO in argon

We present a pseudopotential method to study the absorption spectroscopy of NO in an argon matrix modeled by a large albeit finite cluster. The excited states of NO are described with the virtual orbitals of a NO⁺ Hartree-Fock calculation plus a core-polarization operator to account for the electron-NO⁺ correlation. The argon atoms of the matrix are replaced by pseudopotentials for the repulsive contributions and core-polarization operators to account for matrix polarization and correlation with the excited electron. The model is shown to account for the matrix-induced transition shifts and also for the cut-off of the Rydberg series for n >3 reported in absorption experiments from the ground state. Received: 6 March 1998 / Revised: 1st June 1998 / Accepted: 16 June 1998