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Issue 25, 2006
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Photoelectron imaging following 2 + 1 multiphoton excitation of HBr

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Abstract

The photodissociation and photoionization dynamics of HBr via low-n Rydberg and ion-pair states was studied by using 2 + 1 REMPI spectroscopy and velocity map imaging of photoelectrons. Two-photon excitation at about 9.4–10 eV was used to prepare rotationally selected excited states. Following absorption of the third photon the unperturbed F 1Δ(2) and i 3Δ(2) states ionize directly into the ground vibrational state of the molecular ion according to the Franck–Condon principle and upon preservation of the ion core. In case of the V 1Σ+(0+) ion-pair state and the perturbed E 1Σ+(0+), g 3Σ(0+), and H 1Σ+(0+) Rydberg states the absorption of the third photon additionally results in a long vibrational progression of HBr+ in the X 2Π state as well as formation of electronically excited atomic photofragments. The vibrational excitation of the molecular ion is explained by autoionization of repulsive superexcited states into the ground state of the molecular ion. In contrast to HCl, the perturbed Rydberg states of HBr show strong participation of the direct ionization process, with ionic core preservation.

Graphical abstract: Photoelectron imaging following 2 + 1 multiphoton excitation of HBr

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Publication details

The article was received on 17 Feb 2006, accepted on 06 Apr 2006 and first published on 21 Apr 2006


Article type: Paper
DOI: 10.1039/B602435A
Citation: Phys. Chem. Chem. Phys., 2006,8, 2940-2949

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    Photoelectron imaging following 2 + 1 multiphoton excitation of HBr

    C. Romanescu and H. Loock, Phys. Chem. Chem. Phys., 2006, 8, 2940
    DOI: 10.1039/B602435A

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