Direct readout of excited state lifetimes in chlorin chromophores under electronic strong coupling

TL;DR

This study uses ultrafast spectroscopy to measure excited state lifetimes of chlorin e6 under strong coupling, finding no significant changes compared to free space, thus providing a benchmark for cavity photochemistry theories.

Contribution

It introduces a direct measurement method for excited state lifetimes under strong coupling, revealing unchanged photophysics of chlorin e6, which aids in benchmarking theoretical models.

Findings

No significant change in excited state lifetimes under strong coupling

Method circumvents optical artifacts in ultrafast cavity measurements

Provides a benchmark for cavity photochemistry theories

Abstract

The mechanisms governing molecular photophysics under electronic strong coupling (ESC) remain elusive to date. Here, we use ultrafast pump-probe spectroscopy to study the nonradiative excited state relaxation dynamics of chlorin e6 trimethyl ester (Ce6T) under strong coupling of its transition from the electronic ground state to the Qy band. We use dichroic Fabry-P\'erot cavities to provide a transparent spectral window in which we can directly track the excited state population following optical pumping of either the strongly-coupled Qy band or the higher-lying B band. This scheme circumvents many of the optical artifacts inherent in ultrafast cavity measurements and allows for facile comparison of strongly-coupled measurements with extracavity controls. We observe no significant changes in excited state lifetimes for any optical pumping schemes or cavity coupling conditions considered herein. These results suggest that Ce6T exhibits identical photophysics under ESC and in free space, presenting a new data point for benchmarking emerging theories for cavity photochemistry.