PHYS 1 |
| Recently, Wodtke and collaborators were able to observe cyclic-N3 in the gas-phase as an exclusive photoproduct of the 157 nm photodissociation of ClN3. Understanding the detailed production mechanism of cyclic-N3 is of great importance in high-energy density material (HEDM) chemistry. For this puprose, we have undertaken a theoretical investigation of the photodissociation dynamics of this reaction employing CASSCF, MRCI, CASPT2 and EOM-CCSD methods. The S7 state has been identified as the target excited state in the experiment. After this point, ab initio direct trajectory calculations reveal that the vibrating excited ClN3 goes through a series of conical intersections with lower excited surfaces leading finally to dissociation of the Cl-N bond and subsequent isomerization to the cyclic-N3 isomer. |
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Computational Spectroscopy
8:00 AM-12:05 PM, Sunday, April 6, 2008 Morial Convention Center -- Rm. 342, Oral
Division of Physical Chemistry |