Real-time dynamics of vibronic wavepackets within Rydberg and ion-pair states of molecular iodine - DIRAM
Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2024

Real-time dynamics of vibronic wavepackets within Rydberg and ion-pair states of molecular iodine

Résumé

Real-time dynamics of vibrationally and electronically excited I$_2$ molecules has been investigated experimentally using the pump–probe technique. A 2-photon excitation was performed either at 269 nm or 266 nm. An electronic and vibrational wavepacket was built as coherent superposition of a few (269 nm excitation) or many (266 nm excitation) Rydberg states of the [$^2$π$_3$$_/$$_2$]and [$^2$π$_1$$_/$$_2$]nd series partly coupled with ion-pair states. The probe operated by ionisation or photodetachement. The energy and angular distribution of the resulting photoelectrons, I$^+$ photocations and I$^-$ photoanions were monitored. During the dynamics that is turned on by the pump excitation, the wavepacket splits and explores a variety of electronic states of Rydberg and ion-pair character. The experimental results were complemented by molecular dynamics calculations. This provided invaluable information to identify wavepacket motion along ion-pair potential energy curves.
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Dates et versions

hal-04554044 , version 1 (22-04-2024)

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Jean-Michel Mestdagh, Lou Barreau, Lionel Poisson. Real-time dynamics of vibronic wavepackets within Rydberg and ion-pair states of molecular iodine. Physical Chemistry Chemical Physics, 2024, 26 (15), pp.11516-11530. ⟨10.1039/d4cp00118d⟩. ⟨hal-04554044⟩
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