Anionic states of six-membered aromatic phosphorus heterocycles as studied by electron transmission spectroscopy and ab initio methods

Alberto Modelli, Balázs Hajgató, John F. Nixon, L. Nyulászi

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

The electron transmission spectra of 1,3,5-tri-tert-butylbenzene, 2,4,6-tri-tert-butylpyridine, 2,4,6-tri-tert-butylphosphabenzene, and 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene have been investigated and interpreted by means of quantum chemical calculations. Scaled virtual orbital energies obtained from calculations without employing diffuse functions provide good numerical values for the vertical electron attachment energies (VAEs). B3LYP/6-311+G* VAEs, calculated as the energy difference between the anion and the neutral molecule, were in good agreement with experiment, with the molecules investigated here having VAEs of less than about 1 eV. The first anion state of phosphabenzene is predicted to lie at the edge of stability. The gradual replacement of CH units by phosphorus in π systems results in a significant stabilization of the anionic states, which contrasts with the relative invariance of the electron donor properties. This behavior can be explained by considering that for the P=C π system both the interaction between the atomic levels (β) and the overlap are smaller than for the C=C π system.

Original languageEnglish
Pages (from-to)7440-7447
Number of pages8
JournalJournal of Physical Chemistry A
Volume108
Issue number36
DOIs
Publication statusPublished - Sep 9 2004

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Phosphorus
phosphorus
Spectroscopy
electron attachment
Electrons
spectroscopy
electrons
Anions
energy
anions
Molecules
Invariance
molecules
invariance
Stabilization
stabilization
methylidyne
orbitals
Experiments
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Anionic states of six-membered aromatic phosphorus heterocycles as studied by electron transmission spectroscopy and ab initio methods. / Modelli, Alberto; Hajgató, Balázs; Nixon, John F.; Nyulászi, L.

In: Journal of Physical Chemistry A, Vol. 108, No. 36, 09.09.2004, p. 7440-7447.

Research output: Contribution to journalArticle

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