Bond-length dependence of attosecond ionization delays in O<sub>2</sub> arising from electron correlation to a shape resonance.

Hammerland, Daniel; Berglitsch, Thomas; Zhang, Pengju; Luu, Tran Trung; Ueda, Kiyoshi; Lucchese, Robert R; Wörner, Hans Jakob · Sci Adv · 2024

basic_science · Level V

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Abstract

We experimentally and theoretically demonstrate that electron correlation can cause the bond-length sensitivity of a shape resonance to induce an unexpected vibrational state-dependent ionization delay in a nonresonant channel. This discovery was enabled by a high-resolution attosecond-interferometry experiment based on a 400-nm driving and dressing wavelength. The short-wavelength driver results in a 6.2-electron volt separation between harmonics, markedly reducing the spectral overlap in the measured interferogram. We demonstrate the promise of this method on O<sub>2</sub>, a system characterized by broad vibrational progressions and a dense photoelectron spectrum. We measure a 40-attosecond variation of the photoionization delays over the X<sup>2</sup>Π<i><sub>g</sub></i> vibrational progression. Multichannel calculations show that this variation originates from a strong bond-length dependence of the energetic position of a shape resonance in the [Formula: see text] channel, which translates to the observed effects through electron correlation. The unprecedented energy resolution and delay accuracies demonstrate the promise of visible-light-driven molecular attosecond interferometry.