Time-Domain Rotational Raman Spectroscopy of the Ethylene Dimer and Trimer by Coulomb Explosion Imaging of Rotational Wave Packets.

Abstract

We report rotational Raman spectroscopy of the ethylene dimer and trimer, based on time-resolved Coulomb explosion imaging of rotational wave packets. Rotational wave packets were created in the gas-phase ethylene clusters upon nonresonant ultrashort pulse irradiation. The subsequent rotational dynamics were traced as spatial distribution of monomer ions ejected from the clusters via the Coulomb explosion process induced by a strong probe pulse. The observed images of monomer ions show multiple kinetic energy components. The time-dependence of the angular distribution for each component was analyzed, and the Fourier transformation spectra, which correspond to rotational spectra, were obtained. A lower kinetic energy component was mainly attributed to a signal from the dimer and a higher energy component mainly from the trimer. We have successfully observed rotational wave packets up to a delay time of ∼20 ns and achieved a spectral resolution of 70 MHz after Fourier transformation. Owing to this higher resolution than the previous studies, improved rotational and centrifugal distortion constants were obtained from the spectra. In addition to improving the spectroscopic constants, this study opens the way for rotational spectroscopy of larger molecular clusters than dimers through Coulomb explosion imaging of rotational wave packets. Details of spectral acquisition and analyses of each kinetic energy component are also reported.