Ab initio modeling of optical spectra in pH-sensitive diarylethenes

摘要

The photochromic and acidochromic shifts undergone by recently synthesized diarylethene photochromes have been simulated using a Time-Dependent Density Functional Theory approach relying on a range-separated functional, namely CAM-B3LYP. The selected approach is generally accurate for reproducing the variations of the spectral features, though acidochromic shifts are clearly more challenging than their photochromic counterparts. More importantly, an analyzis of the shapes of the relevant molecular orbitals grants insights into the electro-cyclization of several diarylethenes, therefore partly allowing to understand the presence of experimental deadlocks.