Precise Equilibrium Structure of Benzene
Brian J. Esselman, Maria A. Zdanovskaia, Andrew N. Owen, John F. Stanton, R. Claude Woods, Robert J. McMahon
Abstract
Recent advances in gas-phase structure determination afford outstanding agreement between the CCSD(T)/cc-pCVTZ-corrected semi-experimental ( r e SE ) equilibrium structures and their corresponding best theoretical estimates (BTEs) of the equilibrium structures ( r e ) based upon corrections to the CCSD(T)/cc-pCV5Z geometries for the aromatic heterocycles pyrimidine and pyridazine. Herein, that same analysis is extended to the fundamental aromatic molecule benzene, using published experimental spectroscopic data for a total of 11 available isotopologues. The incorporation of rotational constants from all of these isotopologues and CCSD(T) corrections to address the impacts of both the vibration-rotation interaction and electron-mass distribution results in a highly precise and accurate r e SE structure. The CCSD(T)/cc-pCV5Z optimized geometry has been further corrected to address a finite basis set, untreated electron correlation, relativistic effects, and a breakdown of the Born–Oppenheimer approximation. This analysis achieves outstanding agreement between the r e (BTE) and r e SE structural parameters of benzene to a highly satisfying level (0.0001 Å), an agreement that surpasses our recently published structures of the aforementioned nitrogen-substituted benzene analogues. The D 6 h geometry of benzene is now known to an unprecedented precision: R C–C = 1.3913 (1) Å and R C–H = 1.0809 (1) Å. The mutual agreement between theory and experiment presented in this work validates both, substantially resolving all discrepancies between the r e SE and theoretical r e structures available in the literature.