Two Rydberg states of the NF molecule, the 2 1Δ and 2 1Σ+ states, have been investigated by multiphoton ionization (MPI) spectroscopy. These states are observed via the two-photon resonance enhancements they provide in the multiphoton ionization spectra of NF a 1Δ and NF b 1Σ+. Both states are assigned on the basis of experimental evidence as Rydberg states with the dominant configuration ...1π45σ22π1 (3pπ)1. Ab initio calculations performed at the multireference determinant configuration interaction (MRDCI) level showed that these states were of mixed Rydberg-valence character with the Rydberg character [⋯ 1π45σ2π1 (3pπ)1] dominating at short bond lengths (< 1.35 Å) and the valence character (⋯ 1π35σ22π3) becoming more important at longer bond lengths (> 1.35 Å). These calculations also proved useful in providing a mechanism to account for the rotational predissociation observed in the experimental spectra.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry