Isomerization of Stilbene Using Enforced Geometry Optimization

Using our recently proposed quantum chemical model to simulate the effect of external forces acting on a molecule (Wolinski and Baker, Mol Phys 2009, 107, 2403), which we subsequently termed enforced geometry optimization (EGO), we investigate structural isomerism in C(14)H(12), starting from cis-stilbene. By applying an external force to pairs of carbon atoms, one from each half of the molecule, we have generated 10 different structural isomers. Each was characterized as a minimum by vibrational analysis. Not only can EGO generate potentially new, metastable isomers it can also provide good initial guesses for transition states connecting the starting and final structures, thus giving an estimate of the stability of the new isomers to rearrangement back to the starting material. In addition to the new isomers, we provide a full set of vibrational fundamentals for cis- and trans-stilbene and 4a, 4b-dihydrophenanthrene. The agreement with experimental assignments is excellent, with mean average deviations for the stilbenes of 5.0 cm(-1) or less. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 32: 43-53, 2011