Spectral-to-temporal amplitude mapping polarization spectroscopy of rotational transients

A new implementation of pump-probe polarization spectroscopy is presented where the revivals of an impulsively excited rotational wavepacket are mapped onto a broad-band, chirped continuum pulse to measure a long temporal window without the need for delay scanning. Experimental measurements and a theoretical framework for spectral-temporal amplitude mapping polarization spectroscopy (STAMPS) as applied to impulsive rotational motion are presented. In this technique, a femtosecond laser pulse is used to prepare a rotational wavepacket in a gas-phase sample at room temperature. The rotational revivals of the wavepacket are then mapped onto a chirped continuum (400-800 nm) pulse created by laser filamentation in argon. Nearly single-shot time-resolved rotational spectra are recorded over a 65 ps time window. The transient birefringence spectra are simulated by including terms for polarization rotation of the probe as well as cross-phase modulation. Measurements and simulations are presented for the cylindrically symmetric N2, O2, and CO2 molecules. The long time window of the method allows measurement of rotational spectra for asymmetric top molecules, and here we present measurements for ethylene and methanol.