Photoisomerization pathways of trans-resveratrol

Abstract

Resveratrol is well-known for promoting health benefits due to its antioxidant, anti-aging, anti-carcinogenic, and other beneficial activities. Understanding the photophysics of resveratrol is essential for determining its applicability to pharmaceutical innovations. In the present work, we used an explore-then-assess strategy to map the internal conversion pathways of trans-resveratrol. This strategy consists of exploring the multidimensional configurational space with nonadiabatic dynamics simulations based on a semiempirical multireference method, followed by a feasibility assessment of reduced-dimensionality pathways at a high ab initio theoretical level. The exploration step revealed that internal conversion to the ground state may occur near five distinct conical intersections. The assessment step showed that the main photoisomerization pathway involves a twisted-pyramidalized S₁/S₀ conical intersection, yielding either trans or cis isomers. However, a secondary path was identified, where cis-trans isomerization happens in the excited state and internal conversion occurs at a cyclic conical intersection, yielding a closed-ring resveratrol derivative. This derivative, which can be formed through this direct path or an indirect photoexcitation, may be connected to the production of oxygen-reactive species previously reported and have implications in photodynamic therapy.