Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3

Published

Journal Article

The photodissociation dynamics of chlorine azide (ClN3) at the 157 nm region was studied theoretically using the multireference configuration interaction method and the complete active space self-consistent field direct dynamics method. The excitation at the 157 nm region was assigned to the 4 A1 ′ (S7) X̃ A1 ′ (S0) transition. A likely pathway for the formation of cyclic CN3 after this transition was identified by direct dynamics as follows: ClN3 excited to 4 A1 ′ (S7) dissociates after about 40 fs to excited CN3 (2 A2 ′, with about 44 kcal/mol internal energy) +Cl (P2). This vibrationally hot CN 3 (2 A2 ′) goes diabatically through a conical intersection with CN3 (1 A2 ′) at 44 fs onto 1 A2 ′. At 19 fs later and repeatedly after every 55 fs, CN3 (1 A2 ′) crosses and trickles down via Coriolis coupling to CN3 (2 A2 ″ / B2 1) state, which has a potential minimum at the cyclic- CN3 structure. Some fraction of CN3 (2 A2 ″ / B2 1) produced will survive dissociation and will be found as the cyclic CN3, and some other fraction will eventually dissociate to N (D2) + N2 over a high barrier found previously. © 2008 American Institute of Physics.

Full Text

Duke Authors

Cited Authors

  • Kerkines, ISK; Wang, Z; Zhang, P; Morokuma, K

Published Date

  • November 17, 2008

Published In

Volume / Issue

  • 129 / 17

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.3001918

Citation Source

  • Scopus