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Spectroscopy and thermochemistry of a jet-cooled open-shell polyene: 1,4-pentadienyl radical
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10.1063/1.3640475
/content/aip/journal/jcp/135/12/10.1063/1.3640475
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/12/10.1063/1.3640475

Figures

Image of FIG. 1.
FIG. 1.

(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.

Image of FIG. 2.
FIG. 2.

π molecular orbitals calculated for 1,4-pentadienyl radical. The transition may be described as a superposition of the two one-electron excitations shown.

Image of FIG. 3.
FIG. 3.

The structure and geometric parameters of 1,4-pentadienyl radical. The parameters are listed in the supplementary material. (See Ref. 42.)

Image of FIG. 4.
FIG. 4.

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.

Tables

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Table I.

Calculated excitation energies (eV) for the transition of 1,4-pentadienyl radical.

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Table II.

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.)

Generic image for table
Table III.

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.

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Table IV.

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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/content/aip/journal/jcp/135/12/10.1063/1.3640475
2011-09-28
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Spectroscopy and thermochemistry of a jet-cooled open-shell polyene: 1,4-pentadienyl radical
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/12/10.1063/1.3640475
10.1063/1.3640475
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