Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Photodissociation of phosgene: Theoretical evidence for the ultrafast and synchronous concerted three-body process
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
Show others and affiliations
2009 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 131, no 16Article in journal (Refereed) Published
Abstract [en]

The potential energy surfaces for Cl2CO dissociation into CO+Cl+Cl in the lowest two electronic singlet states (S-0 and S-1) 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 (similar to 40 fs), the photoinitiated dissociation of Cl2CO to CO+2Cl can be considered as the synchronous concerted process.

Place, publisher, year, edition, pages
2009. Vol. 131, no 16
Keyword [en]
3 body decay, initio molecular-dynamics, excited-state topology, sym-triazine, glyoxal photodissociation, dissociation, nm, chloride, photolysis, ethylene
Identifiers
URN: urn:nbn:se:kth:diva-18925DOI: 10.1063/1.3253048ISI: 000271358400034Scopus ID: 2-s2.0-72049092701OAI: oai:DiVA.org:kth-18925DiVA: diva2:336972
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textScopus

Authority records BETA

Luo, Yi

Search in DiVA

By author/editor
Fang, QiuZhang, FengLuo, Yi
By organisation
Theoretical Chemistry
In the same journal
Journal of Chemical Physics

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 123 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf