Bond-length dependence of attosecond ionization delays in O$_{2}$ arising from electron correlation to a shape resonance


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Date

2024-03-29

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Journal Article

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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 O2, a system characterized by broad vibrational progressions and a dense photoelectron spectrum. We measure a 40-attosecond variation of the photoionization delays over the X2Πg 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 b4Σg− 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.

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published

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10 (13)

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AAAS

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03888 - Wörner, Hans Jakob / Wörner, Hans Jakob check_circle

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