Proton Transfer Dynamics in the Aprotic Proton Accepting Solvent 1-Methylimidazole

Thomaz, Joseph E.; Walker, Alice R.; Van Wyck, Stephen J.; Meisner, Jan; Martinez, Todd J.; Fayer, Michael D.

doi:10.1021/acs.jpcb.0c05525

Proton Transfer Dynamics in the Aprotic Proton Accepting Solvent 1-Methylimidazole

Journal Article · Mon Aug 10 00:00:00 EDT 2020 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.0c05525· OSTI ID:1656898

Thomaz, Joseph E. ^[1]; ^[2]; Van Wyck, Stephen J. ^[3]; ^[2]; ^[2]; ^[2]

Stanford Univ., CA (United States); Stanford University, Dept. of Chemistry
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford Univ., CA (United States)

The dynamics of proton transfer to the aprotic solvent 1-methylimidazole (MeIm, proton acceptor) from the photoacid 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HPTS) were investigated using fast fluorescence measurements. The closely related molecule, 8- methoxypyrene-1,3,6-trisulfonic acid trisodium salt (MPTS), which is not a photoacid, was also studied for comparison. Following optical excitation, the wavelength-dependent population dynamics of HPTS in MeIm resulting from the deprotonation process were collected over the entire fluorescence emission window. Analysis of the time-dependent fluorescence spectra revealed four distinct fluorescence bands that appear and decay on different time scales. We label these four states as: protonated (P), associated I (A_I), associated II (A_II), and deprotonated (D). We find that the simple kinetic scheme of P → A_I → A_II → D is not consistent with the data. Instead, the kinetic scheme that describes the data has P decaying into A_I, which mainly goes on to deprotonation (D), but AI can also feed into A_II. A_II can return to A_I or decay to the ground state, but does not deprotonate within experimental error. Finally, quantum chemistry and excitedstate QM/MM Born-Oppenheimer molecular dynamics simulations indicate that A_I and A_II are two H-bonding conformations of MeIm to the HPTS hydroxyl, axial and equatorial, respectively.

View Accepted Manuscript (DOE)

Research Organization:: Stanford University, Stanford California

Sponsoring Organization:: German Research Foundation (DFG); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-84ER13251

OSTI ID:: 1656898

Report Number(s):: DOE-Stanford-ER13251

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 36 Vol. 124; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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