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Updated: Sep 14, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
The strong-field control of IBr photodissociation re-visited
Cristina Sanz-Sanz1, Graham A Worth2
1Departamento de Química Física Aplicada, Módulo 14, Universidad Autónoma de Madrid, 28049 Madrid, Spain. cristina.sanz@uam.es.
Abstract:
The photodissociation of IBr is a paradigm for a process that can be controlled by a strong, non-resonant electric field, known as the non-resonant dynamic stark effect (NRDSE). As shown by B. J. Sussman et al., Science, 2006, 314, 278, a carefully timed intense infra-red pulse can enhance or reduce the flux into the different dissociation channels. This was supported by quantum dynamics simulations using a 3-state model of IBr, but these were unable to reproduce the experimental time-scales. In this paper, we revisit this pump-control scenario using quantum dynamics simulations including all 36-states of IBr in a coupled manifold, with potentials and couplings depending on the applied field strength, i.e. including the light-molecule interaction to all orders. The results reproduce the features of the experimental control, with a better fit to the time-scale than previous simulations. The mechanism by which the control operates is then found be a combination of excited-state excitation and modulation of the avoided crossing on the dissociation pathway.
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