Beyond vinyl: electronic structure of unsaturated propen-1-yl, propen-2-yl, 1-buten-2-yl, and trans-2-buten-2-yl hydrocarbon radicals.
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.
Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
Lucas
L
Koziol
Sergey V
SV
Levchenko
Anna I
AI
Krylov
D000475:Alkenes / Q000737:chemistry; D002073:Butanes / Q000737:chemistry; D004581:Electronics; D005609:Free Radicals / Q000737:chemistry*; D008432:Mathematical Computing; D008958:Models, Molecular; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics; D014753:Vinyl Compounds / Q000737:chemistry*
D000475:Alkenes; D002073:Butanes; D005609:Free Radicals; D014753:Vinyl Compounds; C046888:butane; C013658:propylene