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 S1/T1 intersection structure optimized at the CAS(10,8)/cc-pVDZ level.
Schematically potential energy profiles for the C–Cl (a) and C–C (b) dissociations in the S0, S1, and T1 electronic states with the CCSD/aug-cc-pVDZ calculated relative energies (kcal mol−1), except for the barrier on the subsequent process estimated by the CAS(9,7)/cc-pVDZ calculations.
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 S1 Franck-Condon geometry after photo-excitation at 193 nm. The initial process is shown in the inset.
Time dependence of the fraction of the C–C cleavage for the 138 reactive trajectories leading to 2CO(1Σ) + 2Cl(2 P) along the S0 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.
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 S0 geometry with the total energy conserved at 148.0 kcal mol−1. The initial process is shown in the inset.
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