Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 151, Issue 14, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.5117318
Keywords
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Funding
- U.S. Department of Energy, Office of Science, Basic Energy Science, Chemical Sciences, Geosciences and Biosciences Division [DE-AC02-06CH11357, KC030103172684]
- DOE Office of Science [DE-AC02-06CH11357]
- Office of Biological and Environmental Research
- United States Department of Energy under DOE Contract [DE-AC05-76RL1830]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- Tryggers Science Foundation
- Lendulet (Momentum) Program of the Hungarian Academy of Sciences [LP2013-59]
- Government of Hungary [VEKOP-2.3.2-16-2017-00015]
- European Regional Development Fund [VEKOP-2.3.2-16-2017-00015]
- National Research, Development and Innovation Fund [NKFIH FK 124460]
- European XFEL
- National Science Centre (NCN) in Poland under SONATA BIS 6 Grant [2016/22/E/ST4/00543]
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Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving interest in new means of probing their mechanisms. Using a combination of time-resolved x-ray absorption spectroscopy and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations and x-ray absorption near-edge spectroscopy calculations, we elucidate the mechanism of photoaquation in the model system iron(II) hexacyanide, where UV excitation results in the exchange of a CN- ligand with a water molecule from the solvent. We take advantage of the high flux and stability of synchrotron x-rays to capture high precision x-ray absorption spectra that allow us to overcome the usual limitation of the relatively long x-ray pulses and extract the spectrum of the short-lived intermediate pentacoordinated species. Additionally, we determine its lifetime to be 19 (+/- 5) ps. The QM/MM simulations support our experimental findings and explain the similar to 20 ps time scale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal pentacoordinated geometries, with aquation being only active in the SP configuration.
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