Molecular quantum defect orbital study of the Stark effect in the H3 molecule

Abstract

Stark maps and the distribution of scillator strengths within a Stark manifold in the H3 molecule have been calculated by diagonalization of the Hamiltonian matrix using a molecular quantum defect orbital MQDO basis set. Our perturbative treatment, in which only experimental quantum defects have been used and no fitting parameters are required, explicitly accounts for the coupling between the rotation of the molecular core and the Rydberg-electron motion. A pure Hund’s case d has been adopted for all the Rydberg states except for the np series, for which Hund’s case b is considered to be more realistic. A mixing of some of the np Stark states with those belonging to other Rydberg series appears to occur. The presently achieved results conform very well with other reliable theoretical values, in the absence of experimental data. The adequacy of the MQDO procedure for accurately dealing with properties related to the Stark effect in molecules is suggested.