The photoinduced isomerization mechanism of the 2-(1-(methylimino)methyl)-6-chlorophenol (SMAC): Nonadiabatic surface hopping dynamics simulations.

Abstract

The photophysical properties of the Schiff base family are crucial for their applications such as molecular switches and molecular memories. However, it was found that the photophysical behavior is not uniform for all Schiff base molecules, which shows a significant substituent dependent property. In this article, we studied the photoisomerization mechanism of one Schiff base chlorosubstituted derivative 2-(1-(methylimino)methyl)-6-chlorophenol by employing geometrical optimization, energy profiles scanning, and on-the-fly dynamical simulations. Three types of minimum energy conical intersections were located on the S1/S0 crossing seam, with two characterized by twisting motion of the C=N bond and one featured with the excited state intramolecular proton transfer process and then twisting motion around the C=C bond [excited-state intramolecular proton transfer process (ESIPT)-then-twisting]. By a combination of the dynamics simulation results with the energy profiles scanned along with the ESIPT coordinate, it was found that the photophysical property of the targeted molecule is different from that of most Schiff base members, which prefer to decay by a twisting motion around the C=N bridge bond rather than the ESIPT-then-twisting channel. The minor ESIPT channel is probably governed by a tunneling mechanism. The proposed deactivation mechanism can provide a reasonable explanation for the observations in the experiment and would provide fundamental indications for further design of new and efficient photochromic products.