Abstract

A symmetry concept is proposed that links the presence of vibronic structure in UV-visible spectra in d-systems, with the identification of a single photochemical reaction pathway. It is shown that the vibronic structure on some bands of the Pt(II) D4h complexes is due to the non- degenerate, ungerade b1u (xyz) vibration that points on an intramolecular twisting process for the photochemical cis-trans isomerization. The reaction coordinate is unambiguously defined in a coordinate system where x and y bisect the metal-ligand ML2 angle.

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