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Synchronous concerted multiple-body photodissociation of oxalyl chloride explored by ab initio-based dynamics simulations
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10.1063/1.4812783
/content/aip/journal/jcp/139/2/10.1063/1.4812783
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/2/10.1063/1.4812783
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

Geometric structures of oxalyl chloride in the low-lying electronic states, along with some key bond parameters (bond length in angstrom and bond angle in degree) from the CCSD/cc-pVDZ calculations, except for the S/T intersection structure optimized at the CAS(10,8)/cc-pVDZ level.

Image of FIG. 2.
FIG. 2.

Schematically potential energy profiles for the C–Cl (a) and C–C (b) dissociations in the S, S, and T electronic states with the CCSD/aug-cc-pVDZ calculated relative energies (kcal mol), except for the barrier on the subsequent process estimated by the CAS(9,7)/cc-pVDZ calculations.

Image of FIG. 3.
FIG. 3.

The C–C, C–Cl, and C–O distances and the relative energies of the two lowest singlet states are plotted as a function of time for one representative trajectory of the non-adiabatic four-body dissociation starting from the S Franck-Condon geometry after photo-excitation at 193 nm. The initial process is shown in the inset.

Image of FIG. 4.
FIG. 4.

Time dependence of the fraction of the C–C cleavage for the 138 reactive trajectories leading to 2CO(Σ) + 2Cl( ) along the S pathway (a); the fraction of the C1–Cl5 bond fission (b) and the fraction of the C2–Cl6 bond fission (c) plotted as a function of the time difference between the C–C and C–Cl bond cleavages for the 138 reactive trajectories.

Image of FIG. 5.
FIG. 5.

The C–C, C–Cl, and C–O distances plotted as a function of time for a representative of most trajectories that lead to the three-body dissociation starting from the S geometry with the total energy conserved at 148.0 kcal mol. The initial process is shown in the inset.

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/content/aip/journal/jcp/139/2/10.1063/1.4812783
2013-07-12
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Synchronous concerted multiple-body photodissociation of oxalyl chloride explored by ab initio-based dynamics simulations
http://aip.metastore.ingenta.com/content/aip/journal/jcp/139/2/10.1063/1.4812783
10.1063/1.4812783
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