15min:

AMANDA L. STEBER, JUSTIN L. NEILL, DANIEL P. ZALESKI AND BROOKS H. PATE, Department of Chemistry, University of Virginia, Charlottesville, VA 22904; ALBERTO LESARRI, Departamento Química Física y Química Inorgánica,Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid, Spain.

Phenol dimer has been studied extensively and is considered a benchmark molecular complex for ab initio theory due to a long range dispersion interaction between the rings as well as an intermolecular hydrogen bond. Previously, the structure had been determined using RCS^, and high resolution UV measurements; however, several assumptions were integrated into the structure because a full isotopically substituted structure could not be determined. In this study, the rotational spectrum of the dimer as well as ¹³C and ¹⁸O isotopologue spectra that were seen in natural abundance were obtained using chirped pulse Fourier transform microwave spectroscopy (CP-FTMW). The structure was determined using both linear least squares fitting (r₀ structure) and the Kraitchman substitution analysis (r_s structure). Ab initio calculations were performed for the dimer using MP2/cc-pVTZ cp, B3LYP/6-31G(d,p), M06-2X/6-31G(d,p), and M06-2X/6-311++G(d,p), while CCSD calculations are currently under way. Changing the level of theory and the basis set dramatically changes the structure. The MP2 calculation underestimates the hinge angle (C-O-O-C dihedral angle), while the B3LYP overestimates it. The M06-2X calculations seem to give the best cost-to-benefit ratio when compared to the r_s structure, but they show poorer agreement with increasing basis set size.