University of Connecticut

Events Calendar

PhD Defense

Wednesday, June 27, 2018
12:00pm – 2:00pm

Storrs Campus

Dale L Smith, Department of Physics, University of Connecticut

Velocity Map Imaging of the Single Ionization of Molecular Iodine

Single ionization in molecules is a critical first step in many higher order process such as high harmonic generation. However, single ionization remains poorly understood even in simple diatomic systems. We have found that molecular iodine, I2, has a complicated ionization processes which does not originate from valance orbitals, as would be expected, but from more tightly bound inner orbitals comprised of 5s electrons. I will discuss two experiments which use ultrafast lasers to investigate the ionization of diatomic I2. Ultrafast laser pulses have a duration in the tens of femtoseconds (fs). Since the vibrational period of I2 is ≈180 fs, we are able to ionize the molecule before it dissociates. Velocity map imaging allows us to observe the kinetic energy release (KER) of charged fragments from dissociation after single ionization. In the first experiment, we have performed a wavelength study from 800 to 400 nm. We have found in the I + I+ dissociation channel (which we denote as the (1,0)) the KER of the fragments was mostly inconsistent with ionization to the X-, A-, or B-states of I2+ which implies ionization through deeper orbitals. A pump-probe Fourier technique also showed that modulation in the cation products only occurs below 0.2 eV, which is consistent with dissociation through the B-state and ionization of high-lying molecular orbitals. This rules out a two-step process through the X- and A-states for much of the observed KER. Employing intensity-, polarization-, and wavelength-dependent experiments we were able to eliminate bond softening, electron rescattering, and photon mediation through the X- or A-states. In the second experiment, we performed a detailed wavelength analysis of I2 around its one-photon B-state resonance at 530 nm where we have identified a strong enhancement in the (1,0) channel. The resonance enhancement is found in both ionization from outer orbitals through the B-state as well as ionization from inner orbitals. Interestingly, the branching ratio for inner orbital ionization reaches over 98% at 519 nm and the peaks in the branching ratios of the two channels occur at slightly different wavelengths. For double ionization into an excited state of I2+ we find that the branching ratio closely follows the branching ratio of the single ionization of deeply bound inner orbitals. This implies that excitation of molecules comes about through inner orbital ionization. The finding of these experiments are inconsistent with current tunneling ionization theory which postulates that ionization arises through the least bound, outer orbital electrons.


Prof. G. Gibson

Physics Department (primary)

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