|Title||Resonance-enhanced multiphoton ionization spectroscopy of the nf molecule - (1)sigma(+) and (1)delta 3p rydberg states|
|Publication Type||Journal Article|
|Year of Publication||1993|
|Authors||Dyke, JM, Keszthelyi, T, Lee, EPF, Low, RJ, Richter, R|
|Journal||Journal of Chemical Physics|
Two Rydberg states of the NF molecule, the 2 1DELTA and 2 1SIGMA+ 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 1DELTA and NF b 1SIGMA+. Both states are assigned on the basis of experimental evidence as Rydberg states with the dominant configuration ...1pi(4)5sigma(2)2pi1 (3ppi)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 [...1pi(4)5sigma(2)2pi1 (3ppi)1] dominating at short bond lengths (< 1.35 angstrom) and the valence character (...1pi(3)5sigma(2)2pi3) becoming more important at longer bond lengths (> 1.35 angstrom). These calculations also proved useful in providing a mechanism to account for the rotational predissociation observed in the experimental spectra.