Mass-Correlated High-Resolution Spectra and the Structure of Benzene

J Phys Chem Lett. 2022 Sep 8;13(35):8278-8283. doi: 10.1021/acs.jpclett.2c02035. Epub 2022 Aug 29.

Abstract

Mass-correlated rotational alignment spectroscopy resolved the rotational Raman spectra for 5 benzene isotopologues with unprecedented resolution. 13-C isotopologues were characterized at natural abundance. Fitted rotational constants allowed the analysis of effective and equilibrium bond lengths for benzene with sub-mÅ uncertainties. We found that previously reported experimental structures were wrong by multiple mÅ, due to unrecognized H/D isotope effects. Our results also refute recent experimental and theoretical literature claims of identical effective C-H and C-D bond lengths in benzene and reveal an isotope effect similar to that in other small molecules.