Non-polaritonic effects in cavity-modified photochemistry

Abstract

Strong coupling of molecules to vacuum fields has been widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. Here we re-examine the first of these vacuum-modified chemistry experiments, in which changes to a molecular photoisomerisation process were attributed to strong coupling of the molecules to visible light. We observed significant variations in photoisomerisation rates for molecules placed in a variety of optical cavity structures, but found no evidence that these changes need to be attributed to strong coupling. Instead, we suggest that the photoisomerisation rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. Our results indicate that care must be taken to rule out non-polaritonic effects before invoking strong coupling to explain any changes of chemical properties arising in cavity-based experiments.Comment: 31 pages, 16 figure