Abstract
The first vacuum-ultraviolet absorption spectrum of pyridine-N-oxide has been obtained, and has led to the identification of nearly 30 Rydberg states. These states were identified by use of the vibrational envelope ("footprint") of the UV-photoelectron spectrum, and are based on the first to the third ionization energies (IE). The adiabatic IE order, central to the Rydberg state symmetry identification, is confirmed by multi-configuration SCF calculations as: 12B1 < 12B2 < 12A2 < 22B1. Several excited valence state equilibrium structures were determined by multi-configuration SCF and coupled cluster procedures. Multi-reference multi-root CI was used to calculate both Rydberg and valence state vertical excitation energies and oscillator strengths, which were correlated with the experimental measurements.
Original language | English (US) |
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Article number | 214317 |
Journal | Journal of Chemical Physics |
Volume | 138 |
Issue number | 21 |
DOIs | |
State | Published - Jun 7 2013 |
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry