PMID- 25715942
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20150511
LR  - 20150312
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 17
IP  - 12
DP  - 2015 Mar 28
TI  - Characterization of molecular channel in photodissociation of SOCl2 at 248 nm: 
      Cl2 probing by cavity ring-down absorption spectroscopy.
PG  - 7838-47
LID - 10.1039/c4cp06043a [doi]
AB  - A primary elimination channel of the chlorine molecule in the one-photon 
      dissociation of SOCl2 at 248 nm was investigated using cavity ring-down 
      absorption spectroscopy (CRDS). By means of spectral simulation, the ratio of the 
      vibrational population in the v = 0, 1, and 2 levels was evaluated to be 
      1 : (0.10 +/- 0.02) : (0.009 +/- 0.005), corresponding to a Boltzmann vibrational 
      temperature of 340 +/- 30 K. The Cl2 molecular channel was obtained with a quantum 
      yield of 0.4 +/- 0.2 from the X(1)A' ground state of SOCl2via internal conversion. 
      The dissociation mechanism differs from a prior study where a smaller yield of 
      <3% was obtained, initiated from the 2(1)A' excited state. Temperature-dependence 
      measurements of the Cl2 fragment turn out to support our mechanism. With the aid 
      of ab initio potential energy calculations, two dissociation routes to the 
      molecular products were found, including one synchronous dissociation pathway via 
      a three-center transition state (TS) and the other sequential dissociation 
      pathway via a roaming-mediated isomerization TS. The latter mechanism with a 
      lower energy barrier dominates the dissociation reaction.
FAU - Chen, Bo-Jung
AU  - Chen BJ
AD  - Department of Chemistry, National Taiwan University, Taipei, Taiwan. 
      kclin@ntu.edu.tw.
FAU - Tsai, Po-Yu
AU  - Tsai PY
FAU - Huang, Ting-Kang
AU  - Huang TK
FAU - Xia, Zhu-Hong
AU  - Xia ZH
FAU - Lin, King-Chuen
AU  - Lin KC
FAU - Chiou, Chuei-Jhih
AU  - Chiou CJ
FAU - Sun, Bing-Jian
AU  - Sun BJ
FAU - Chang, A H H
AU  - Chang AH
LA  - eng
PT  - Journal Article
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
EDAT- 2015/02/27 06:00
MHDA- 2015/02/27 06:01
CRDT- 2015/02/27 06:00
PHST- 2015/02/27 06:00 [entrez]
PHST- 2015/02/27 06:00 [pubmed]
PHST- 2015/02/27 06:01 [medline]
AID - 10.1039/c4cp06043a [doi]
PST - ppublish
SO  - Phys Chem Chem Phys. 2015 Mar 28;17(12):7838-47. doi: 10.1039/c4cp06043a.