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⇱ Photodissociation dynamics of bromoiodomethane from the first and second absorption bands. A combined velocity map and slice imaging study - Physical Chemistry Chemical Physics (RSC Publishing)


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From the journal:

Physical Chemistry Chemical Physics


Photodissociation dynamics of bromoiodomethane from the first and second absorption bands. A combined velocity map and slice imaging study

Author affiliations

* Corresponding authors

a Departamento de Qumica Fsica I, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
E-mail: lbanares@ucm.es
Tel: +34 913944228

b Departamento de Qumica, Módulo 13, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid, Spain
E-mail: jesus.gonzalezv@uam.es

c Institute for Advanced Research in Chemical Sciences (IAdChem), Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid, Spain

Abstract

The photodissociation dynamics of bromoiodomethane (CH2BrI) have been investigated at the maximum of the first A and second A′ absorption bands, at 266 and 210 nm excitation wavelengths, respectively, using velocity map and slice imaging techniques in combination with a probe detection of both iodine and bromine fragments, I(2P3/2), I*(2P1/2), Br(2P3/2) and Br*(2P1/2) via (2 + 1) resonance enhanced multiphoton ionization. Experimental results, i.e. translational energy and angular distributions, are reported and discussed in conjunction with high level ab initio calculations of potential energy curves and absorption spectra. The results indicate that in the A-band, direct dissociation through the 5A′ excited state leads to the I(2P3/2) channel while I*(2P1/2) atoms are produced via the 5A′ → 4A′/4A′′ nonadiabatic crossing. The presence of Br and Br* fragments upon excitation to the A-band is attributed to indirect dissociation via a curve crossing between the 5A′ with upper excited states such as the 9A′. The A′-band is characterized by a strong photoselectivity leading exclusively to the Br(2P3/2) and Br*(2P1/2) channels, which are likely produced by dissociation through the 9A′ excited state. Avoided crossings between several excited states from both the A and A′ bands entangle however the possible reaction pathways.

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Supplementary files

Article information

Article type
Paper
Submitted
17 Oct 2017
Accepted
22 Dec 2017
First published
03 Jan 2018
Phys. Chem. Chem. Phys., 2018,20, 3490-3503
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Photodissociation dynamics of bromoiodomethane from the first and second absorption bands. A combined velocity map and slice imaging study

S. Marggi Poullain, D. V. Chicharro, E. Navarro, L. Rubio-Lago, J. González-Vázquez and L. Bañares, Phys. Chem. Chem. Phys., 2018, 20, 3490 DOI: 10.1039/C7CP07077B

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