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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I2_wavepacket_dynamics-2.pdf (5.92 Mo)
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I2_wavepacket_dynamics_ESI.pdf (1.61 Mo)
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