Theoretical Study of the Fast Photodissociation Channels of the Monohalobenzenes
(2004) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 108(12). p.2339-2345- Abstract
- Excited state properties of fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene have been investigated theoretically using multireference CASSCF and CASPT2 methods. Experimentally, chlorobenzene and bromobenzene are known to exhibit one fast dissociation channel, whereas iodobenzene exhibits two fast dissociation channels. The calculations indicate that the chlorobenzene, the bromobenzene, and the slower iodobenzene dissociation channels are due to intersystem crossings from a bound (π,π*) singlet excited state to a repulsive (n,σ*) triplet excited state. The faster iodobenzene dissociation channel is instead found to be caused by a direct dissociation of an antibonding (n,σ*) singlet excited state. The CASPT2 calculations predict... (More)
- Excited state properties of fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene have been investigated theoretically using multireference CASSCF and CASPT2 methods. Experimentally, chlorobenzene and bromobenzene are known to exhibit one fast dissociation channel, whereas iodobenzene exhibits two fast dissociation channels. The calculations indicate that the chlorobenzene, the bromobenzene, and the slower iodobenzene dissociation channels are due to intersystem crossings from a bound (π,π*) singlet excited state to a repulsive (n,σ*) triplet excited state. The faster iodobenzene dissociation channel is instead found to be caused by a direct dissociation of an antibonding (n,σ*) singlet excited state. The CASPT2 calculations predict that the onset of fluorobenzene photodissociation should occur around 196 nm, with a single time constant longer than 1 ns. CASSCF geometries and accurate MSCASPT2 calculated vertical excitation energies are presented for the ground state as well as the first excited singlet and triplet states of all the monohalobenzenes. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1457785
- author
- Liu, Y.-J. ; Persson, Petter LU and Lunell, S.
- publishing date
- 2004
- type
- Contribution to journal
- publication status
- published
- subject
- in
- The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
- volume
- 108
- issue
- 12
- pages
- 2339 - 2345
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:1842636265
- ISSN
- 1520-5215
- DOI
- 10.1021/jp0379648
- language
- English
- LU publication?
- no
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 2745fd19-cb86-417f-a019-4cf30a682a52 (old id 1457785)
- date added to LUP
- 2016-04-01 16:36:41
- date last changed
- 2022-03-22 19:53:03
@article{2745fd19-cb86-417f-a019-4cf30a682a52, abstract = {{Excited state properties of fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene have been investigated theoretically using multireference CASSCF and CASPT2 methods. Experimentally, chlorobenzene and bromobenzene are known to exhibit one fast dissociation channel, whereas iodobenzene exhibits two fast dissociation channels. The calculations indicate that the chlorobenzene, the bromobenzene, and the slower iodobenzene dissociation channels are due to intersystem crossings from a bound (π,π*) singlet excited state to a repulsive (n,σ*) triplet excited state. The faster iodobenzene dissociation channel is instead found to be caused by a direct dissociation of an antibonding (n,σ*) singlet excited state. The CASPT2 calculations predict that the onset of fluorobenzene photodissociation should occur around 196 nm, with a single time constant longer than 1 ns. CASSCF geometries and accurate MSCASPT2 calculated vertical excitation energies are presented for the ground state as well as the first excited singlet and triplet states of all the monohalobenzenes.}}, author = {{Liu, Y.-J. and Persson, Petter and Lunell, S.}}, issn = {{1520-5215}}, language = {{eng}}, number = {{12}}, pages = {{2339--2345}}, publisher = {{The American Chemical Society (ACS)}}, series = {{The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory}}, title = {{Theoretical Study of the Fast Photodissociation Channels of the Monohalobenzenes}}, url = {{http://dx.doi.org/10.1021/jp0379648}}, doi = {{10.1021/jp0379648}}, volume = {{108}}, year = {{2004}}, }