Abstract: | The rotational barriers of overcrowded PCBs are predicted by ab initio methods including electron correlation, thus settling the controversy between theory and experiment. For 2,2′,3,3′,4,6′-hexachlorobiphenyl ( PCB 132 ), an enantiomerization barrier of 185 kJ/mol is calculated by B3LYP/6-31G*, in excellent agreement with the experimental data. Chirality 9:350–353, 1997. © 1997 Wiley-Liss, Inc. |