title: Assessing the role of moment of inertia in optical Kerr effect spectroscopy.
abstract: Optical Kerr effect (OKE) spectroscopy allows for the acquisition of high-quality, Bose-Einstein-corrected, low-frequency Raman spectra in liquids. However, the assignment of a molecular interpretation to these spectra remains an open problem. To address this issue, here we present an OKE study of benzene and four of its isotopologues. Our results indicate that hindered rotations are the major contributor to the OKE reduced spectral density (RSD) over the entire intermolecular spectral region (0-250 cm(-1)). We also have found that isotopologues with six (13)C atoms have RSDs that are enhanced at frequencies below 30 cm(-1). We further demonstrate that the collective orientational correlation time of these liquids scales with the inverse square root of the tumbling moment of inertia, indicating that there is strong translation-rotation coupling in benzene.
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
authors.forename: Katherine
authors.initials: K
authors.lastname: Manfred
authors.forename: XiaoXiao
authors.initials: X
authors.lastname: He
authors.forename: John T
authors.initials: JT
authors.lastname: Fourkas