TY  - JOUR
A1  - Norell, Jesper
A1  - Eckert, Sebastian
A1  - Van Kuiken, Benjamin E.
A1  - Föhlisch, Alexander
A1  - Odelius, Michael
T1  - Ab initio simulations of complementary K-edges and solvatization effects for detection of proton transfer in aqueous 2-thiopyridone
T2  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - The nitrogen and sulfur K-edge X-ray absorption spectra of aqueous 2-thiopyridone, a model system for excited-state proton transfer in several recent time-resolved measurements, have been simulated from ab initio molecular dynamics. Spectral signatures of the local intra- and inter-molecular structure are identified and rationalized, which facilitates experimental interpretation and optimization. In particular, comparison of aqueous and gas phase spectrum simulations assesses the previously unquantified solvatization effects, where hydrogen bonding is found to yield solvatochromatic shifts up to nearly 1 eV of the main peak positions. Thereby, while each K-edge can still decisively determine the local protonation of its core-excited site, only their combined, complementary fingerprints allow separating all of the three relevant molecular forms, giving a complete picture of the proton transfer.
Y1  - 2019
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/48130
SN  - 0021-9606
SN  - 1089-7690
VL  - 151
IS  - 11
PB  - American Institute of Physics
CY  - Melville
ER  -