Skip to main content

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

Publication ,  Journal Article
Kerkines, ISK; Wang, Z; Zhang, P; Morokuma, K
Published in: Journal of Chemical Physics
November 17, 2008

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.

Duke Scholars

Published In

Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

November 17, 2008

Volume

129

Issue

17

Related Subject Headings

  • Chemical Physics
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Kerkines, I. S. K., Wang, Z., Zhang, P., & Morokuma, K. (2008). Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3. Journal of Chemical Physics, 129(17). https://doi.org/10.1063/1.3001918
Kerkines, I. S. K., Z. Wang, P. Zhang, and K. Morokuma. “Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3.” Journal of Chemical Physics 129, no. 17 (November 17, 2008). https://doi.org/10.1063/1.3001918.
Kerkines ISK, Wang Z, Zhang P, Morokuma K. Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3. Journal of Chemical Physics. 2008 Nov 17;129(17).
Kerkines, I. S. K., et al. “Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3.” Journal of Chemical Physics, vol. 129, no. 17, Nov. 2008. Scopus, doi:10.1063/1.3001918.
Kerkines ISK, Wang Z, Zhang P, Morokuma K. Photodissociation of ClN3 at 157 nm: Theory suggests a pathway leading to cyclic CN3. Journal of Chemical Physics. 2008 Nov 17;129(17).

Published In

Journal of Chemical Physics

DOI

ISSN

0021-9606

Publication Date

November 17, 2008

Volume

129

Issue

17

Related Subject Headings

  • Chemical Physics
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences