Eur. Phys. J. D 4, 219-224 (1998)
https://doi.org/10.1007/s100530050202

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

Laboratoire de Physique Quantique (UMR 5626 CNRS) , IRSAMC Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France

Corresponding author: ^a spiegel@irsamcl.ups-tlse.fr

Received: 6 March 1998
Revised: 1 June 1998
Accepted: 16 June 1998
Published online: 15 November 1998

Abstract

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.