Photon Echo Spectroscopy in the Single Optical-Cycle Regime

A very high temporal resolution and a broad bandwidth are but two advantages provided by the use of extremely short sub-5-fs pulses in a nonlinear spectroscopic experiment. However, the applicability of the standard theoretical description becomes questionable for the pulses that consist merely of a couple of optical oscillations. Far instance, the conventionally employed slowly varying envelope approximation, implying that the change of the pulse amplitude on the duration of an optical cycle is negligible compared to the magnitude of the amplitude itself, can no longer be maintained. Furthermore, the phase-matching bandwidth that is limited due to dispersion in the nonlinear medium rapidly gains importance with the increase of the spectral width of the pulse. Another point of serious concern is the frequency-dependent variation in the sensitivity of signal photodetectors. In combination, these features result in what is known as a spectral-filter effect. Finally, artificial lengthening of the experimental transients is a direct consequence of the noncollinear geometry employed in spectroscopic experiments. We present a theoretical analysis which thoroughly reexamines the formalism of ultrafast photon echo spectroscopy. We obtain a general expression for the echo signal, which is valid even for single-cycle-pulse applications. The derived formalism is applied to photon-echo spectroscopy on the hydrated electron with 5-fs pulses

Wave Packet Dynamics in Ultrafast Spectroscopy of the Hydrated Electron

Hydrated-electron dynamics is examined by frequency-resolved pump-probe experiments using pulses of 13 fs centered at 780 nm. A recurrence at ~40 fs signifies a strong coupling of the electronic transition to underdamped solvent motions. Wave packet dynamics launched by the pump pulse produces an ultrafast red-shift of the electronic transition by approximately 6500 cm-1. Gross features of the pump-probe experiments are analyzed using a two-level system