The electronic states of pyridine-N-oxide studied by VUV photoabsorption and ab initio configuration interaction computations

Michael H. Palmer, Søren Vrønning Hoffmann, Nykola C. Jones, Elliott R. Smith, Dennis L Lichtenberger

Research output: Contribution to journalArticle

6 Citations (Scopus)

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 languageEnglish (US)
Article number214317
JournalThe Journal of Chemical Physics
Volume138
Issue number21
DOIs
StatePublished - Jun 7 2013

Fingerprint

Rydberg states
Ionization potential
Electronic states
photoabsorption
Vacuum
configuration interaction
pyridines
self consistent fields
oxides
Excitation energy
Crystal symmetry
Photoelectrons
electronics
valence
Absorption spectra
ionization
ultraviolet absorption
ultraviolet spectra
footprints
configurations

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

The electronic states of pyridine-N-oxide studied by VUV photoabsorption and ab initio configuration interaction computations. / Palmer, Michael H.; Hoffmann, Søren Vrønning; Jones, Nykola C.; Smith, Elliott R.; Lichtenberger, Dennis L.

In: The Journal of Chemical Physics, Vol. 138, No. 21, 214317, 07.06.2013.

Research output: Contribution to journalArticle

Palmer, Michael H. ; Hoffmann, Søren Vrønning ; Jones, Nykola C. ; Smith, Elliott R. ; Lichtenberger, Dennis L. / The electronic states of pyridine-N-oxide studied by VUV photoabsorption and ab initio configuration interaction computations. In: The Journal of Chemical Physics. 2013 ; Vol. 138, No. 21.
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