The electronic states of buta-1,3-diene studied by ab initio configuration interaction and DFT methods, and electron energy loss spectroscopy

Michael H. Palmer, Isobel C. Walker

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

The electronic vertical excitation energies for singlet and triplet valence, and Rydberg states of trans-buta-1,3-diene have been computed using ab initio multi-reference multi-root CI procedures with a [4s3p3d3f] set of Rydberg functions. Close numerical agreement between theory and experiment was found for a number of low-lying electronic states. The present CI and CASSCF [8MO,8e] calculations suggest that both the vertical and adiabatic order of the valence (pp) states is: A1Ag<B1Bu. An electron energy-loss spectrum, reported here, in which the incident electrons have near-threshold energies, supports this order. Adiabatic excitation energies and structures were obtained for several singlet and triplet states using CASSCF and B3LYP procedures; the results from these methods are generally in good agreement with each other. The C1C2 to C2C3 bond length ratio in the excited states varies widely, and is discussed. © 2010 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)159-169
Number of pages11
JournalChemical Physics
Volume373
Issue number3
DOIs
Publication statusPublished - 3 Aug 2010

Keywords

  • Buta-1,3-diene: energy levels
  • EEL spectrum
  • Excited state energies and structures
  • Photoelectron spectrum
  • VUV spectrum

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