10.1021/acs.jpcb.7b09688.s001
Christoph J. Sahle
Christoph J.
Sahle
Johannes Niskanen
Johannes
Niskanen
Christian Schmidt
Christian
Schmidt
Johannes Stefanski
Johannes
Stefanski
Keith Gilmore
Keith
Gilmore
Yury Forov
Yury
Forov
Sandro Jahn
Sandro
Jahn
Max Wilke
Max
Wilke
Christian Sternemann
Christian
Sternemann
Cation Hydration in Supercritical NaOH and HCl Aqueous
Solutions
American Chemical Society
2017
fingerprinting analysis
NaOH molecules
HCl Aqueous Solutions
hydrogen-bonding topology
oxygen atoms
ab initio
simulation results
Experimental nonresonant X-ray Raman
Cation Hydration
Supercritical NaOH
oxygen K-edge show
water structure
solution
dynamics simulations
core-level spectra
hydration shells
2017-11-21 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Cation_Hydration_in_Supercritical_NaOH_and_HCl_Aqueous_Solutions/5682688
We present a study of the local atomic
environment of the oxygen
atoms in the aqueous solutions of NaOH and HCl under simultaneous
high-temperature and high-pressure conditions. Experimental nonresonant
X-ray Raman scattering core-level spectra at the oxygen K-edge show
systematic changes as a function of temperature and pressure. These
systematic changes are distinct for the two different solutes and
are described well by calculations within the BetheāSalpeter
formalism for snapshots from ab initio molecular dynamics simulations.
The agreement between experimental and simulation results allows us
to use the computations for a detailed fingerprinting analysis in
an effort to elucidate the local atomic structure and hydrogen-bonding
topology in these relevant solutions. We observe that both electrolytes,
especially NaOH, enhance hydrogen bonding and tetrahedrality in the
water structure at supercritical conditions, in particular in the
vicinity of the hydration shells. This effect is accompanied with
the association of the HCl and NaOH molecules at elevated temperatures.