Snyder Joshua A, Bragg Arthur E
Department of Chemistry , Johns Hopkins University , 3400 North Charles Street , Baltimore , Maryland 21218 , United States.
J Phys Chem Lett. 2018 Oct 4;9(19):5847-5854. doi: 10.1021/acs.jpclett.8b02489. Epub 2018 Sep 25.
We demonstrate pump-repump-probe (PRP) transient hole burning as a spectroscopic tool for differentiating reactive from nonreactive deactivation of excited photochemical reactants observed by transient absorption spectroscopy (TAS). This method utilizes a time-delayed, wavelength-tunable ultrafast pulse to alter the excited reactant population, with the impact of "repumping" quantified through depletions in photoproduct absorption. We apply this approach to characterize dynamics affecting the nonadiabatic photocyclization efficiency to form S dihydrotriphenylene (DHT) following 266 nm excitation of ortho-terphenyl (OTP). TAS studies revealed bimodal deactivation of OTP*, but neither relaxation time scale (700 fs and 3.0 ps) could be assigned unambiguously to DHT formation due to overlap of excited-state and product spectra. PRP studies reveal that S OTP only cyclizes on the slower of these time scales, with the faster process attributable to nonreactive deactivation. We demonstrate that this method offers greater photochemical insights without assuming models to globally fit spectral transients collected by TAS.
