Beyond vinyl: electronic structure of unsaturated propen-1-yl, propen-2-yl, 1-buten-2-yl, and trans-2-buten-2-yl hydrocarbon radicals

J Phys Chem A. 2006 Mar 2;110(8):2746-58. doi: 10.1021/jp055375r.

Abstract

Vertical excitation energies and oscillator strengths for several valence and Rydberg electronic states of vinyl, propen-1-yl, propen-2-yl, 1-buten-2-yl, and trans-2-buten-2-yl radicals are calculated using the equation-of-motion coupled cluster methods with single and double substitutions (EOM-CCSD). The ground and the lowest excited state (n <-- pi) equilibrium geometries are calculated using the CCSD(T) and EOM-SF-CCSD methods, respectively, and adiabatic excitation energies for the n <-- pi state are reported. Systematic changes in the geometries, excitation energies, and Rydberg state quantum defects within this group of radicals are discussed.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Alkenes / chemistry
  • Butanes / chemistry
  • Electronics
  • Free Radicals / chemistry*
  • Mathematical Computing
  • Models, Molecular
  • Quantum Theory
  • Stereoisomerism
  • Thermodynamics
  • Vinyl Compounds / chemistry*

Substances

  • Alkenes
  • Butanes
  • Free Radicals
  • Vinyl Compounds
  • butane
  • propylene