Femtosecond pump/supercontinuum-probe spectroscopy: Optimized setup and signal analysis for single-shot spectral referencing

A setup for pump/supercontinuum-probe spectroscopy is described which (i) is optimized to cancel fluctuations of the probe light by single-shot referencing, and (ii) extends the probe range into the near-uv (1000-270 nm). Reflective optics allow 50 mu m spot size in the sample and upon entry into two separate spectrographs. The correlation gamma(same) between sample and reference readings of probe light level at every pixel exceeds 0.99, compared to gamma(consec) <0.92 reported for consecutive referencing. Statistical analysis provides the confidence interval of the induced optical density, Delta OD. For demonstration we first examine a dye (Hoechst 33258) bound in the minor groove of double-stranded DNA. A weak 1.1 ps spectral oscillation in the fluorescence region, assigned to DNA breathing, is shown to be significant. A second example concerns the weak vibrational structure around t=0 which reflects stimulated Raman processes. With 1% fluctuations of probe power, baseline noise for a transient absorption spectrum becomes 25 mu OD rms in 1 s at 1 kHz, allowing to record resonance Raman spectra of flavine adenine dinucleotide in the S(0) and S(1) state. (C) 2010 American Institute of Physics. [doi:10.1063/1.3492897]