Pump–supercontinuum-probe (PSCP) spectroscopy with femtosecond time resolution is developed theoretically and experimentally. The connection to previous theoretical results on nonchirped probing is established. It is experimentally shown that the supercontinuum can be described as a single chirped pulse. A key problem of the technique—the precise time correction of transient spectra—is solved by monitoring the nonresonant electronic response from a pure solvent (liquids) or from a transparent substrate (solid films). This allows for an adequate characterization of the supercontinuum, in particular, for directly measuring the spectral dependence of the pump-probe cross correlation. For 50-fs pump pulses, a theoretical estimate gives an accuracy for the time correction of 10 fs, which is typically ≈1/30 of the supercontinuum pulse duration. Hence a time resolution of 10–20 fs can be experimentally realized. Contributions to the nonresonant transient signal from high-frequency Raman excitations and from low-frequency impulsive-stimulated Raman processes are discussed. The PSCP technique is illustrated by results from experiments with fused silica and several common solvents and with a chromophore in solution.

• Received 25 June 1998

DOI:https://doi.org/10.1103/PhysRevA.59.2369