Characterizing Slow Photochemical Reaction Kinetics by Enhanced Sampling of Rare Events with Capillary Optical Fibers and Kramers’ Theory

[Image: see text] Characterization of slow chemical reactions is essential for assessing catalytic efficiency in chemistry and biology. Traditionally, chemical reaction rates are obtained from population relaxation kinetics measurements and the Arrhenius equation. Unfortunately, it is difficult to use this approach to characterize reactions wherein concentrations change slowly. Thus, it is interesting to see whether a dynamical view of chemical reactions may be used to obtain the reaction rates of slow processes. In the present work, we perform Brownian dynamics simulations of an asymmetric double-well potential to investigate how enhanced sampling of barrier crossing at transition states improves the characterization of reaction rate constants. We then present the design of a liquid-filled capillary optical fiber-based fluorescence spectrometer, which, like rare events, is also based on Poissonian statistics. We use the instrument to characterize the slow photochemical degradation kinetics of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) in o-dichlorobenzene. We have employed in situ optical microscopy measurements and electrodynamics simulations to characterize the excitation beam profile inside a liquid-filled capillary fiber. We compare the cuvette and capillary fiber sample holders and show that the MEH-PPV fluorescence line shape is independent of the sample holder, as expected. We characterize the photochemical degradation kinetics of MEH-PPV in o-dichlorobenzene solutions placed in the cuvette versus that in the capillary fiber. We observe small and slow changes in the time-dependent fluorescence spectra when the degradation reaction is performed in the cuvette. On the other hand, we are able to characterize reactant-concentration decay and product-concentration buildup from the time-dependent fluorescence spectra recorded during photochemical degradation of MEH-PPV performed inside the capillary optical fiber. Ultrafast optically heterodyne-detected optical Kerr effect spectroscopy and multimode Brownian oscillator analysis provide further insights into the role of bath oscillator modes of friction in the mechanism of MEH-PPV photochemical degradation. Overall, the work presented herein shows that slow photochemical degradation kinetics of MEH-PPV can be successfully and efficiently assessed in the capillary fiber fluorescence spectrometer.