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Title: Elucidation of the photoaquation reaction mechanism in ferrous hexacyanide using synchrotron x-rays with sub-pulse-duration sensitivity

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5117318· OSTI ID:1608558
ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [3];  [2]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [4]; ORCiD logo [2];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  3. Lund Univ. (Sweden)
  4. European X-ray Free-Electron Laser (XFEL), Hamburg (Germany)
  5. Hungarian Academy Sciences, Budapest (Hungary). Wigner Research Centre for Physics
+ Show Author Affiliations

Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving an interest in new means of probing their mechanisms. In this work, using a combination of timeresolved x-ray absorption spectroscopy (XAS) and hybrid quantum mechanical, molecular mechanics (QM/MM) molecular dynamics (MD) simulations and x-ray absorption nearedge spectroscopy (XANES) 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 and kinetic fits suggest a formation time of 1.5 (0.6) ps. The QM/MM simulations support our experimental findings and explain the ~20 ps timescale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal (TBP) pentacoordinated geometries, with aquation being only active in the SP configuration.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER); Tryggers Science Foundation; Hungarian Academy of Sciences; Government of Hungary; European Regional Development Fund (ERDF); Hungarian National Research, Development and Innovation Office (NRDI); European XFEL; National Science Centre (NCN)
Grant/Contract Number:
AC05-76RL01830; AC02-06CH11357; KC030103172684; AC02-05CH11231; LP2013-59; VEKOP-2.3.2-16-2017-00015; NKFIH FK 124460; 2016/22/E/ST4/00543; AC05-76RL1830
OSTI ID:
1608558
Alternate ID(s):
OSTI ID: 1570031; OSTI ID: 1607390
Report Number(s):
PNNL-SA-144898; TRN: US2104924
Journal Information:
Journal of Chemical Physics, Vol. 151, Issue 14; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

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Cited By (1)

X-ray tracking of structural changes during a subnanosecond solid-solid phase transition in cobalt nanoparticles journal December 2019

Figures / Tables (8)

FIG. 1(p. 10)figure FIG. 1
FIG. 2(p. 11)figure FIG. 2
FIG. 3(p. 12)figure FIG. 3
FIG. 4(p. 14)figure FIG. 4
FIG. 5(p. 16)figure FIG. 5
FIG. 6(p. 17)figure FIG. 6
FIG. 7(p. 18)figure FIG. 7
FIG. 8(p. 19)figure FIG. 8

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Synchrotrons
Quantum mechanical/molecular mechanical calculations
Laser physics
Triplet state
Molecular dynamics
Substitution reactions
Density functional theory
X-ray absorption spectroscopy
Photochemical reactions
Free electron lasers