PMID- 30278130
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20181026
LR  - 20181026
IS  - 1520-5215 (Electronic)
IS  - 1089-5639 (Linking)
VI  - 122
IP  - 42
DP  - 2018 Oct 25
TI  - Cavity Ring-Down Absorption Spectroscopy: Optical Characterization of ICl Product 
      in Photodissociation of CH(2)ICl at 248 nm.
PG  - 8344-8353
LID - 10.1021/acs.jpca.8b07012 [doi]
AB  - Iodine monochloride (ICl) elimination from one-photon dissociation of CH(2)ICl at 
      248 nm is monitored by cavity ring-down absorption spectroscopy (CRDS). The 
      spectrum of ICl is acquired in the transition of B(3)Pi(0) <-- X(1)Sigma(+) and is 
      confirmed to result from a primary photodissociation, that is, CH(2)ICl + hnu --> 
      CH(2) + ICl. The vibrational population ratio is determined with the aid of 
      spectral simulation to be 1:(0.36 +/- 0.10):(0.11 +/- 0.05) for the vibrational 
      levels nu = 0, 1, and 2 in the ground electronic state, corresponding to a 
      Boltzmann-like vibrational temperature of 535 +/- 69 K. The quantum yield of the 
      ICl molecular channel for the reaction is obtained to be 0.052 +/- 0.026 using a 
      relative method in which the scheme CH(2)Br(2) --> CH(2) + Br(2) is adopted as the 
      reference reaction. The ICl product contributed by the secondary collisions is 
      minimized such that its quantum yield obtained is not overestimated. With the aid 
      of the CCSD(T)//B3LYP/MIDI! level of theory, the ICl elimination from CH(2)ICl is 
      evaluated to follow three pathways via either (1) a three-center transition state 
      or (2) two isomerization transition states. However, the three-center concerted 
      mechanism is verified to be unfavorable.
FAU - Paredes-Roibas, Denis
AU  - Paredes-Roibas D
AD  - Departamento de Ciencias y Tecnicas Fisicoquimicas , Facultad de Ciencias, 
      Universidad Nacional de Educacion a Distancia (UNED) , Paseo de la Senda del Rey 
      9 , E-28040 Madrid , Spain.
FAU - Balaganesh, Muthiah
AU  - Balaganesh M
AD  - Department of Chemistry , National Taiwan Univeristy , Taipei 10617 , Taiwan.
AD  - Institute of Atomic and Molecular Sciences , Academia Sinica , Taipei 10617 , 
      Taiwan.
FAU - Kasai, Toshio
AU  - Kasai T
AD  - Department of Chemistry , National Taiwan Univeristy , Taipei 10617 , Taiwan.
AD  - Institute of Scientific and Industrial Research , Osaka University , Ibaraki, 
      Osaka 567-0047 , Japan.
FAU - Gavira-Vallejo, Jose Maria
AU  - Gavira-Vallejo JM
AD  - Departamento de Ciencias y Tecnicas Fisicoquimicas , Facultad de Ciencias, 
      Universidad Nacional de Educacion a Distancia (UNED) , Paseo de la Senda del Rey 
      9 , E-28040 Madrid , Spain.
FAU - Lin, King Chuen
AU  - Lin KC
AUID- ORCID: 0000-0002-4933-7566
AD  - Department of Chemistry , National Taiwan Univeristy , Taipei 10617 , Taiwan.
AD  - Institute of Atomic and Molecular Sciences , Academia Sinica , Taipei 10617 , 
      Taiwan.
LA  - eng
PT  - Journal Article
DEP - 20181016
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
EDAT- 2018/10/03 06:00
MHDA- 2018/10/03 06:01
CRDT- 2018/10/03 06:00
PHST- 2018/10/03 06:00 [pubmed]
PHST- 2018/10/03 06:01 [medline]
PHST- 2018/10/03 06:00 [entrez]
AID - 10.1021/acs.jpca.8b07012 [doi]
PST - ppublish
SO  - J Phys Chem A. 2018 Oct 25;122(42):8344-8353. doi: 10.1021/acs.jpca.8b07012. Epub 
      2018 Oct 16.