It has been proposed that the pseudo-Jahn-Teller effect (PJTE) is the only source of symmetry breaking in molecules with a nondegenerate electronic ground state. The result of this process yields an equilibrium molecular geometry that is distorted from a symmetric configuration. We have investigated the effects of the pseudo-Jahn-Teller effect on malonaldehyde and on cyclobutane. The equilibrium structure of malonaldehyde exhibits Cs symmetry, which is lowered from a potential C2v symmetric structure due to the asymmetric position of the intramolecular hydrogen bonding H atom. Similarly, the equilibrium structure of cyclobutane exhibits D2d symmetry, which is lowered from a potential D4h planar structure due to ring puckering. The properties of several derivatives with substitutions modifying the electronic structure of the molecule were computed in order to investigate the PJTE effect on these molecules. These derivatives were prepared so as to maintain the overall point group symmetry of the molecule. The results of these calculations on the molecular orbitals of the electronic ground state and excited electronic state purported to be responsible for the PJTE energy lowering will be presented.

Computational investigation of the pseudo-Jahn-Teller effect on malonaldehyde and cyclobutane

255th National Meeting (2018)

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