Wide-range IR spectra of diarylethene derivatives and their simulation using the density functional theory

Diarylethenes (DAEs), promising photochromic molecular switches, undergo pericyclic reactions upon ultraviolet or visible light illumination. For this reason, most studies on DAEs employ UV-vis spectroscopies. However, also their infrared (IR) spectra are valuable, in particular, for understanding the vibrational dynamics which accompanies the relevant photoreactions. An accurate assignment of IR bands to molecular modes can be achieved through a comparison between experimental and computed theoretical spectra. Even though more sophisticated computational methods are available, the density functional theory (DFT) is usually employed for this task, because of its modest cost and versatility. Here, we have tested the ability of several DFT functionals to reproduce the wide-range, 400-3200 cm^-1, IR spectra of open and closed isomers of four representative DAE molecules. We find that global and range-separated, corrected for anharmonicity by scaling factors, hybrid DFT functionals are able to reproduce the IR spectra of DAEs, however, instead of the popular B3LYP functional we propose the use of the dispersion-corrected PBE0 functional. The paper also proposes a semi-automatic method of band assignment.