Further evidence for resonant photoelectron-solvent scattering in nitrous oxide cluster anions.
The effects of anion solvation by N(2)O on photoelectron angular distributions are revisited in light of new photoelectron imaging results for the NO(-)(N(2)O)(n), n = 0-4 cluster anions at 266 nm. The new observations are examined in the context of the previous studies of O(-) and NO(-) anions solvated in the gas phase by nitrous oxide [Pichugin; et al. J. Chem. Phys. et al. 2008, 129, 044311.; Velarde; et al. J. Chem. Phys. et al. 2007, 127, 084302.]. The photoelectron angular distributions collected in the three separate studies are summarized and analyzed using bare O(-) and NO(-) as zero-solvation references. Solvent-induced deviations of the angular distributions from the zero-solvation reference are scaled by solvation number (n) to yield solvent-induced anisotropy differentials. These differentials, calculated identically for the O(-)(N(2)O)(n) and NO(-)(N(2)O)(n) cluster series, show remarkably similar energy dependences, peaking in the vicinity of a known electron-N(2)O scattering resonance. The results support the conclusion that the solvation effect on the photoelectron angular distributions in these cases is primarily due to resonant interaction of photoelectrons with the N(2)O solvent, rather than a solvent-induced perturbation of the parent-anion electronic wave function.
Grumbling
Emily R
ER
Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721-0041, USA.
Pichugin
Kostyantyn
K
Velarde
Luis
L
Sanov
Andrei
A