Effect of load-resisting force on photoisomerization mechanism of a single second generation light-driven molecular rotary motor.

Abstract

A pivotal aspect of molecular motors is their capability to generate load capacity from a single entity. However, few studies have directly characterized the load-resisting force of a single light-driven molecular motor. This research provides a simulation analysis of the load-resisting force for a highly efficient, second-generation molecular motor developed by Feringa et al. We investigate the M-to-P photoinduced nonadiabatic molecular dynamics of 9-(2,3-dihydro-2-methyl-1H-benz[e]inden-1-ylidene)-9H-fluorene utilizing Tully's surface hopping method at the semi-empirical OM2/MRCI level under varying load-resisting forces. The findings indicate that the quantum yield remains relatively stable under forces up to 0.003a.u., with the photoisomerization mechanism functioning typically. Beyond this threshold, the quantum yield declines, and an alternative photoisomerization mechanism emerges, characterized by an inversion of the central double bond's twisting direction. The photoisomerization process stalls when the force attains a critical value of 0.012a.u. Moreover, the average lifetime of the excited state oscillates around that of the unperturbed system. The quantum yield and mean lifetime of the S1 excited state in the absence of external force are recorded at 0.54 and 877.9fs, respectively. In addition, we analyze a time-dependent fluorescence radiation spectrum, confirming the presence of a dark state and significant vibrations, as previously observed experimentally by Conyard et al.