Measuring autoionization decay lifetimes of optically forbidden inner valence excited states in neon atoms with attosecond noncollinear four wave mixing spectroscopy

TL;DR

This study uses attosecond noncollinear four wave mixing spectroscopy to measure autoionization decay lifetimes of inner valence excited states in neon, combining experimental data with ab initio calculations to understand electron correlation effects.

Contribution

It introduces a novel spectroscopic method to measure ultrafast decay lifetimes of inner valence states in neon and validates the results with two independent theoretical approaches.

Findings

Measured lifetimes: 7 fs, 48 fs, 427 fs for 3s, 3p, 3d states

Experimental results agree with ab initio calculations

Longer lifetimes correlate with higher angular momentum states

Abstract

Attosecond noncollinear four wave mixing spectroscopy with one attosecond extreme ultraviolet (XUV) pulse and two few-cycle near-infrared (NIR) pulses was used to measure the autoionization decay lifetimes of inner valence electronic excitations in neon atoms. After a 43-48 eV XUV photon excites a 2s electron into the 2s2p6[np] Rydberg series, broadband NIR pulses couple the 2s2p6[3p] XUV-bright state to neighboring 2s2p6[3s] and 2s2p6[3d] XUV-dark states. Controllable delays of one or both NIR pulses with respect to the attosecond XUV pulse reveal the temporal evolution of either the dark or bright states, respectively. Experimental lifetimes for the 3s, 3p, and 3d states are measured to be 7 +/- 2 fs, 48 +/- 8 fs, and 427 +/- 40 fs, respectively, with 95% confidence. Accompanying calculations with two independent ab initio theoretical methods, NewStock and ASTRA, verify the findings. The results support the expected trend that the autoionization lifetime should be longer for states that have a smaller penetration in the radial region of the 2s core hole, which in this case is for the higher angular momentum Rydberg orbitals. The underlying theory thus links the lifetime results to electron correlation and provides an assessment of the direct and exchange terms in the autoionization process.