Excited-State Proton Transfer of Photoexcited Pyranine in Water Observed by Femtosecond Stimulated Raman Spectroscopy Public Deposited

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  • We use femtosecond stimulated Raman spectroscopy (FSRS) to illuminate the choreography of intermolecular excited-state proton transfer (ESPT) of photoacid pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, HPTS) in water. The multidimensional reaction coordinate responsible for photoacidity is revealed to involve sequential activation of characteristic skeletal motions during the ca. 1 ps preparation stage preceding ESPT. The initial ring-coplanarity breaking follows in-plane ring breathing (191 cm⁻¹), and is facilitated by HPTS ring wagging (108 cm⁻¹) and ring-H out-of-plane motions (321, 362, 952 cm⁻¹), which largely decay within ~1 ps. ESPT then occurs with intrinsic inhomogeneity via various number of intervening water molecules over relatively larger distances than those in acetate-water system. The intricate relationship between the time-resolved excited-state vibrational modes of HPTS reveals the essential role of coherent low-frequency skeletal motions gating ESPT, and the multi-staged proton-transfer process having the kinetic isotope effect (KIE) value of 3–4 in aqueous solution on the 5–200 ps timescale.
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  • F. Han, W. Liu, C. Fang, Excited-State Proton Transfer of Photoexcited Pyranine in Water Observed by Femtosecond Stimulated Raman Spectroscopy, Chemical Physics (2013), doi: http://dx.doi.org/ 10.1016/j.chemphys.2013.03.009
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  • description.provenance : Submitted by Deanne Bruner (deanne.bruner@oregonstate.edu) on 2013-10-21T21:51:12Z No. of bitstreams: 1 FangChongChemistryExcitedStateProton.pdf: 1279164 bytes, checksum: a1f8704d5bee25642c53d97037e79162 (MD5)
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