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Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy.
Loe, Caroline M; Liekhus-Schmaltz, Chelsea; Govind, Niranjan; Khalil, Munira.
Afiliación
  • Loe CM; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
  • Liekhus-Schmaltz C; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
  • Govind N; Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
  • Khalil M; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
J Phys Chem Lett ; 12(40): 9840-9847, 2021 Oct 14.
Article en En | MEDLINE | ID: mdl-34606267
Excited-state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specific and enables direct, individual probes of the proton-donating and -accepting atoms. Herein, we report a computational study to resolve the ESIPT in 10-hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound. We use linear-response time-dependent density functional theory (LR-TDDFT) combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge, paving the way for future experiments at X-ray free electron lasers.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem Lett Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem Lett Año: 2021 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos