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Updated: Jun 8, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Exploring wavepacket dynamics behind strong-field momentum-dependent photodissociation in CH(2)BrI(+)
Jesús González-Vázquez1, Leticia González, Sarah R Nichols
1Institut für Physikalische Chemie, Friedrich-Schiller Universität Jena, Helmholzweg 4, 07743 Jena, Germany.
Abstract:
The ultrafast photodissociation dynamics of CH(2)BrI(+) into CH(2)Br(+) + I is studied using high level ab initio electronic structure calculations in conjunction with integration of the time-dependent Schrödinger equation and compared with measured pump-probe signals. These pump-probe measurements provide evidence for momentum-dependent dissociation, which is interpreted using two theoretical models. The first is based on DFT and TD-DFT calculations neglecting spin-orbit coupling, while the other, more rigorous model employs a larger number of coupled multi-configurational potentials obtained by means of CASSCF calculations. The latter model highlights the role of spin-orbit coupling between ionic electronic states as well as the effect of strong fields in the quantum dynamics including Stark-shifts and multi-photon excitation.
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