uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Photochemistry of Bromofluorobenzenes
Show others and affiliations
2006 In: Journal of Physical Chemistry A, Vol. 110, 7045- p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
2006. Vol. 110, 7045- p.
URN: urn:nbn:se:uu:diva-96969OAI: oai:DiVA.org:uu-96969DiVA: diva2:171722
Available from: 2008-04-02 Created: 2008-04-02Bibliographically approved
In thesis
1. Photochemistry of Phenyl Halides
Open this publication in new window or tab >>Photochemistry of Phenyl Halides
2008 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

We have studied fundamental aspects of photo-induced dissociation kinetics and dynamics in several phenyl halides. By combining femtosecond pump-probe measurements with ab initio calculations we are able to account for several observations. In mixed phenyl halides, the dissociation kinetics is found to be dependent on the nature, the number, and the position of the substituents, and also on the excitation wavelength. A surprisingly large reduction in the dissociation time constant, compared to that of bromobenzene (~30 ps), is observed when having two or more fluorine atoms. For example, in bromopentafluorobenzene a subpicosecond time constant is obtained. This can be explained by a significant lowering of the repulsive potential energy curves (PEC) along the C-Br bond. However, several of the experimental results cannot be accounted for by one-dimensional PECs. Therefore, we suggest a refined model for the dissociation, in which the excited states of the same spin multiplicity are coupled by employing multidimensional potential energy surfaces. This model has been explicitly evaluated by quantum dynamics simulations in the case of 3-BrFPh, and it seems to be capable of capturing the main features in the measured kinetics. Thereby we are also able to clarify the role of spin-orbit coupling in these molecules.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2008. 57 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 417
Chemistry, Photochemistry, Predissociation, Phenyl halides, Excited states, Substituent effects, Pump-probe spectroscopy, Molecular beam, Dynamics, Kemi
National Category
Chemical Sciences
urn:nbn:se:uu:diva-8602 (URN)978-91-554-7146-0 (ISBN)
Public defence
2008-04-24, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Available from: 2008-04-02 Created: 2008-04-02 Last updated: 2011-03-14Bibliographically approved

Open Access in DiVA

No full text

By organisation
Department of Physical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Total: 202 hits
ReferencesLink to record
Permanent link

Direct link