Wavelength-Dependent Photodissociation of Benzoic Acid Monomer in alpha C-O Fission
2010 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 114, no 1, 680-684 p.Article in journal (Refereed) Published
In concert with the latest laser-induced fluorescence (LIF) experiment [Wei et al. J. Phys. Client. A 2008, 112, 4727], we investigated the photodissociation mechanics of the benzoic acid monomer (BAM) with alpha C-O fission by means of state-of-the-art ab initio calculations. Complete active space self-consistent-field (CASSCF) and multi reference CASSCF second-order perturbation theory (MSCASPT2) calculations were performed on the ground and a number of low-lying excited states of BAM. Our calculations indicated that alpha C-O fission from the S, state is in competition with the fission from the T-2 state upon the 266-284 nm wavelength photon. This differs from the conclusion of the previous theoretical investigation and clarified the vague experimental conclusion made earlier. According to Our calculations, alpha C-O fission mainly occurs at the T, state upon photoexcitation at 284-294 nm, and the photon with a wavelength longer than 294 nm is unable to present the alpha C-O fission. This conclusion agrees with the LIF experimental observation.
Place, publisher, year, edition, pages
2010. Vol. 114, no 1, 680-684 p.
193 NM, PERTURBATION-THEORY, ACETIC-ACID, DYNAMICS, DECARBOXYLATION, PRODUCT, DISSOCIATION, SPECTROSCOPY, MECHANISMS, PHOTOLYSIS
IdentifiersURN: urn:nbn:se:kth:diva-29076DOI: 10.1021/jp908567mISI: 000273268900081ScopusID: 2-s2.0-75249092144OAI: oai:DiVA.org:kth-29076DiVA: diva2:391873
QC 201101252011-01-252011-01-252011-05-20Bibliographically approved