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Photodissociation of phosgene: Theoretical evidence for the ultrafast and synchronous concerted three-body process

J. Chem. Phys. 131, 164306 (2009); doi:10.1063/1.3253048

Published 30 October 2009

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Qiu Fang,1,2 Feng Zhang,1,2 Lin Shen,1 Wei-Hai Fang,1 and Yi Luo2
1College of Chemistry, Beijing Normal University, Beijing 100875, China
2Department of Theoretical Chemistry, School of Biotechnology, Royal Institute of Technology, S-10691 Stockholm, Sweden
The potential energy surfaces for Cl2CO dissociation into CO+Cl+Cl in the lowest two electronic singlet states (S0 and S1) have been determined by the complete active space self-consistent field, coupled-cluster method with single and double excitations (CCSD), and equation-of-motion CCSD calculations, which are followed by direct ab initio molecular dynamics simulations to explore its photodissociation dynamics at 230 nm. It is found that the C–O stretching mode is initially excited upon irradiation and the excess internal energies are transferred to the C–Cl symmetric stretching mode within 200 fs. On average, the first and the second C–Cl bonds break completely within subsequent 60 and 100 fs, respectively. Electronic structure and dynamics calculations have thus provided a strong evidence that the photoinitiated dissociation of Cl2CO at 230 nm or shorter wavelengths is an ultrafast, adiabatic, and concerted three-body process. Since the two C–Cl bonds begin to break at the same time and the time interval between the two C–Cl bond broken fully is very short (~40  fs), the photoinitiated dissociation of Cl2CO to CO+2Cl can be considered as the synchronous concerted process. ©2009 American Institute of Physics
History: Received 9 August 2009; accepted 30 September 2009; published 30 October 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/164306/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.50.-m
    Photochemistry
  • 82.20.Kh
    Potential energy surfaces for chemical reactions
  • 82.20.Wt
    Computational modeling and simulation of chemical kinetics
  • YEAR: 2009

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ISSN:
0021-9606 (print)   1089-7690 (online)
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