Structure of benzene from mass-correlated rotational Raman spectroscopy

We present high resolution rotational Raman spectra and derived geometry parameters for benzene. Rotational Raman spectra with sub-5 MHz resolution were obtained via high-resolution mass-correlated rotational alignment spectroscopy. Isotopologue spectra for C(6)H(6), (13)C–C(5)H(6), C(6)D(6), and (13)C–C(5)D(6) were distinguished through their correlated mass information. Spectra for (13)C(6)H(6) were obtained with lower resolution. Equilibrium and effective bond lengths were estimated from measured inertial moments, based on explicit assumptions and approximations. We discuss the origin of significant bias in previously published geometry parameters and the possibility to derive H,D isotope-specific bond lengths from purely experimental data.