Experimental and theoretical studies of the valence-shell dipole excitation spectrum of molecular fluorine

Electron energy loss measurements and concommitant RPAE calculations are reported of the valence-shell dipole excitation spectrum of molecular fluorine. The measured spectrum is dominated by a series of strong features in the 12–16 eV interval which are in accord with X1Σg+→1Σu+ bands assigned in a previously reported high-resolution optical study. These features are attributed on basis of the present RPAE calculations to configuration mixing between 1πg→npπu Rydberg and 3σg→3σu intravalence excitations. A depleted X→Vσ charge-transfer excitation is correspondingly observed at ≈17 eV, in good accord with the calculated values. The appearance of the σ→σ* transition in F2 below the 3σg−1 threshold is in marked contrast to the situation in other light diatomic molecules, in which cases σ→σ* transitions appear as intravalence shape resonances in photoionization continua. Assignments are also provided of weak, irregularly spaced X1Σg+→1Πu excitations the origins of which are attributed to configuration mixing between 1πg→npσu and 1πu→nsσg Rydberg series.