Localization effects in the Auger spectra of ring nitrogen systems: Pyridine, poly(2-vinyl)pyridine, borazine, and boron nitride

Journal Article · Wed Apr 15 04:00:00 EDT 1987 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.451900· OSTI ID:6736247

Rye, R R; Kelber, J A; Kellogg, G E; Nebesny, K W; Lichtenberger, D L

The N(KVV) Auger spectra of gas phase pyridine (C/sub 5/H/sub 5/N) and borazine (B/sub 3/N/sub 3/H/sub 6/), and of solid phase poly(2-vinyl)pyridine (PVP) and hexagonal boron nitride ((BN)/sub x/) are reported and analyzed. The data indicate two Auger ''fingerprint'' types of nitrogen. Ammonia (NH/sub 3/) is the prototype for the first, where three of the five valence electrons are sigma bonding and the other two are the lone pair. This localized electronic structure gives rise to relatively sharp features in the N(KVV) spectrum. Typical of the second fingerprint type is pyridine, where there are two sigma bonding electrons, a lone pair of electrons, and one electron contributing to the delocalized ..pi.. system. Theoretical nitrogen Auger transition energies and intensities are calculated for pyridine to demonstrate the general origin of the overlapping features in the relatively broad N(KVV) spectrum of this molecule. PVP fits into the second fingerprint type while borazine and boron nitride give nitrogen Auger spectra more like ammonia. Approximate calculations using the equivalent core concept are used to clarify the relationship between the ammonia, borazine, and boron nitride spectra. It is shown that in these systems the initial Auger state (core--hole) largely localizes the bonds and lone pair on the nitrogen. The Auger spectra show that it is the sigma, ..pi.. and nonbonding orbital characters that provide the Auger fingerprint.

• Research Organization: Sandia National Laboratories, Albuquerque, New Mexico 87185
• DOE Contract Number: AC02-80ER10746
• OSTI ID: 6736247
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 86:8; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
AROMATICS
AUGER EFFECT
AUGER ELECTRON SPECTROSCOPY
AZINES
BORON COMPOUNDS
BORON NITRIDES
CHEMICAL ANALYSIS
CHEMICAL BONDS
ELECTRON SPECTROSCOPY
ELECTRONIC STRUCTURE
HETEROCYCLIC COMPOUNDS
INNER-SHELL IONIZATION
IONIZATION
NITRIDES
NITROGEN COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PNICTIDES
PYRIDINES
SPECTROSCOPY