Spin-orbit ab initio study of alkyl halide dissociation via electronic curve crossing
(2004) In Journal of Chemical Physics 121(12). p.5761-5766- Abstract
- An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased... (More)
- An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased intersystem crossing probability on fluorination. We also report the potential curves and the region of curve crossing for CH3Br and CH3Cl. (C) 2004 American Institute of Physics. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/138941
- author
- Ajitha, D ; Wierzbowska, M ; Lindh, Roland LU and Malmqvist, Per-Åke LU
- organization
- publishing date
- 2004
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 121
- issue
- 12
- pages
- 5761 - 5766
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000223872000023
- scopus:5544229534
- pmid:15367000
- ISSN
- 0021-9606
- DOI
- 10.1063/1.1784411
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039), Chemical Physics (S) (011001060)
- id
- 61d66df8-15f4-4a05-b143-4f8d60100499 (old id 138941)
- date added to LUP
- 2016-04-01 12:17:29
- date last changed
- 2023-01-03 06:26:44
@article{61d66df8-15f4-4a05-b143-4f8d60100499, abstract = {{An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased intersystem crossing probability on fluorination. We also report the potential curves and the region of curve crossing for CH3Br and CH3Cl. (C) 2004 American Institute of Physics.}}, author = {{Ajitha, D and Wierzbowska, M and Lindh, Roland and Malmqvist, Per-Åke}}, issn = {{0021-9606}}, language = {{eng}}, number = {{12}}, pages = {{5761--5766}}, publisher = {{American Institute of Physics (AIP)}}, series = {{Journal of Chemical Physics}}, title = {{Spin-orbit ab initio study of alkyl halide dissociation via electronic curve crossing}}, url = {{http://dx.doi.org/10.1063/1.1784411}}, doi = {{10.1063/1.1784411}}, volume = {{121}}, year = {{2004}}, }