(Top) The R2C2PI spectrum observed on m/z 67, from an electrical discharge containing 1,4-pentadiene. (Bottom) A fully ab initio Franck-Condon simulation, including Dushinsky mixing. Assignments are made to the experimental spectrum guided by the simulation.
π molecular orbitals calculated for 1,4-pentadienyl radical. The ← transition may be described as a superposition of the two one-electron excitations shown.
The structure and geometric parameters of 1,4-pentadienyl radical. The parameters are listed in the supplementary material. (See Ref. 42.)
The frontier orbital energies as a function of the a 2 outer-bond torsion (ν14). Upon electronic excitation, the force constant for this motion halves.
Calculated excitation energies (eV) for the ← transition of 1,4-pentadienyl radical.
Selected calculated vibrational frequencies (cm−1) for 1,4-pentadienyl radical in the ground and first excited electronic states. Experimentally derived values are given for comparison, with the more tentative values in parentheses. A full listing of calculated frequencies is available in the supplementary material. (See Ref. 42.)
Observed and calculated vibronic band positions, in cm−1, relative to the origin band at 19 449 cm−1, in the state of 1,4-pentadienyl radical.
Calculated G3X(MP2)-RAD total energies (0 K, Hartrees) and various relative energies (kJ mol−1) for radicals and corresponding precursor molecules.
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