Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 41, 2007
Previous Article Next Article

Multiphoton dissociation dynamics of BrCl and the BrCl+ cation

Author affiliations

Abstract

Ion imaging methods have enabled identification of three mechanisms by which 79Br+ and 35Cl+ fragment ions are formed following one-color multiphoton excitation of BrCl molecules in the wavelength range 324.6 > λ > 311.7 nm. Two-photon excitation within this range populates selected vibrational levels (v′ = 0–5) of the [X 2Π1/2]5sσ Rydberg state. Absorption of a third photon results in branching between (i) photoionization (i.e. removal of the Rydberg electron—a traditional 2 + 1 REMPI process) and (ii) π* ← π excitation within the core, resulting in formation of one or more super-excited states with Ω = 1 and configuration [A 2Π1/2]5sσ. The fate of the latter states involves a further branching. They can autoionize (yielding BrCl+(X 2Π) ions in a wider range of v+ states than formed by direct 2 + 1 REMPI). Further, one-photon absorption by the parent ions resulting from direct ionization or autoionization leads to formation of Br+ and (energy permitting) Cl+ fragment ions. Alternatively, the super-excited molecules can fragment to neutral atoms, one of which is in a Rydberg state. Complementary ab initio calculations lead to the conclusion that the observed [Cl**[3PJ]4s + Br/Br*] products result from direct dissociation of the photo-prepared super-excited states, whereas [Br**[3PJ]5p + Cl/Cl*] product formation involves interaction between the [A 2Π1/2]5sσ and [X 2Π1/2]5pσ Rydberg potentials at extended Br–Cl bond lengths. Absorption of one further photon by the resulting Br** and Cl** Rydberg atoms leads to their ionization, and thus their appearance in the Br+ and Cl+ fragment ion images.

Graphical abstract: Multiphoton dissociation dynamics of BrCl and the BrCl+ cation

Back to tab navigation
Please wait while Download options loads

Publication details

The article was received on 19 Jun 2007, accepted on 27 Jul 2007 and first published on 30 Aug 2007


Article type: Paper
DOI: 10.1039/B709222A
Citation: Phys. Chem. Chem. Phys., 2007,9, 5531-5541
  •   Request permissions

    Multiphoton dissociation dynamics of BrCl and the BrCl+ cation

    O. P. J. Vieuxmaire, N. Hendrik Nahler, R. N. Dixon and M. N. R. Ashfold, Phys. Chem. Chem. Phys., 2007, 9, 5531
    DOI: 10.1039/B709222A

Search articles by author