Ultra-broadband transient absorption down to 200 nm enabled by soliton dynamics in gas-filled hollow capillary fibers

Abstract

The deep ultraviolet (DUV) window (200-300 nm) is essential for the characterization of (bio)chemical and material systems through the UV signatures of nucleobases, amino acids, peptide bonds, many organic moieties, and wide bandgap transitions. However, extending ultrafast spectroscopy to the DUV to access the associated electronic and structural dynamics has largely remained elusive, due to the limited bandwidth and efficiency of common femtosecond DUV pulse sources. We now close this gap and demonstrate ultra-broadband femtosecond transient absorption (TA) spanning 200-800 nm, achieving unprecedented coverage of the entire DUV window. We generate supercontinuum probe pulses through soliton self-compression in a helium-filled hollow capillary fiber at a repetition rate of 20 kHz and fully suppress their high intrinsic intensity fluctuations via a correlation matrix referencing scheme. We thus achieve detector-noise-limited TA measurements with an exceptional resolution of 9 $μ$OD in one second, and demonstrate these novel capabilities by resolving the ultrafast spin-crossover dynamics of a Fe(II) complex in the DUV. This work opens the path to unravel previously inaccessible photophysical and photochemical dynamics encoded in the DUV.