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Simkovitch R, Akulov K, Shomer S, et al. Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint. J Phys Chem A. 2014;118(25):4425-43doi: 10.1021/jp5002435.
Simkovitch, R., Akulov, K., Shomer, S., Roth, M. E., Shabat, D., Schwartz, T., & Huppert, D. (2014). Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint. The journal of physical chemistry. A, 118(25), 4425-43. https://doi.org/10.1021/jp5002435
Simkovitch, Ron, et al. "Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint." The journal of physical chemistry. A vol. 118,25 (2014): 4425-43. doi: https://doi.org/10.1021/jp5002435
Simkovitch R, Akulov K, Shomer S, Roth ME, Shabat D, Schwartz T, Huppert D. Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint. J Phys Chem A. 2014 Jun 26;118(25):4425-43. doi: 10.1021/jp5002435. Epub 2014 Jun 12. PMID: 24870027.
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J Phys Chem A. 2014 Jun 26;118(25):4425-43. doi: 10.1021/jp5002435. Epub 2014 Jun 12.

Comprehensive study of ultrafast excited-state proton transfer in water and D2O providing the missing RO(-)···H(+) ion-pair fingerprint.

The journal of physical chemistry. A

Ron Simkovitch, Katherine Akulov, Shay Shomer, Michal E Roth, Doron Shabat, Tal Schwartz, Dan Huppert

Affiliations

  1. Raymond and Beverly Sackler Faculty of Exact Sciences, School of Chemistry, Tel Aviv University , Tel Aviv 69978, Israel.

PMID: 24870027 DOI: 10.1021/jp5002435

Abstract

Steady-state and time-resolved optical techniques were employed to study the photoprotolytic mechanism of a general photoacid. Previously, a general scheme was suggested that includes an intermediate product that, up until now, had not been clearly observed experimentally. For our study, we used quinone cyanine 7 (QCy7) and QCy9, the strongest photoacids synthesized so far, to look for the missing intermediate product of an excited-state proton transfer to the solvent. Low-temperature steady-state emission spectra of both QCy7 and QCy9 clearly show an emission band at T < 165 K in H2O ice that could be assigned to ion-pair RO(-)*···H3O(+), the missing intermediate. Room-temperature femtosecond pump-probe spectroscopy transient spectra at short times (t < 4 ps) also shows the existence of transient absorption and emission bands that we assigned to the RO(-)*···H3O(+) ion pair. The intermediate dissociates on a time scale of 1 ps and about 1.5 ps in H2O and D2O samples, respectively.

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