Ion pairing in water solutions alters both the water hydrogen-bond network and ion solvation, modifying the dynamics and properties of electrolyte water solutions. Here, we report an anomalous intrinsic fluorescence of KCl aqueous solution at room temperature and show that its intensity increases with the salt concentration. From the ab initio density functional theory (DFT) and time-dependent DFT modeling, we propose that the fluorescence emission could originate from the stiffening of the hydrogen bond network in the hydration shell of solvated ion-pairs that suppresses the fast nonradiative decay and allows the slower radiative channel to become a possible decay pathway. Because computations suggest that the fluorophores are the local ion-water structures present in the prenucleation phase, this band could be the signature of the incoming salt precipitation.

Villa, A., Doglia, S., De Gioia, L., Natalello, A., Bertini, L. (2022). Fluorescence of KCl Aqueous Solution: A Possible Spectroscopic Signature of Nucleation. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 126(13), 2564-2572 [10.1021/acs.jpcb.2c01496].

Fluorescence of KCl Aqueous Solution: A Possible Spectroscopic Signature of Nucleation

Villa A. M.
Primo
;
De Gioia L.;Natalello A.
Penultimo
;
Bertini L.
Ultimo
2022

Abstract

Ion pairing in water solutions alters both the water hydrogen-bond network and ion solvation, modifying the dynamics and properties of electrolyte water solutions. Here, we report an anomalous intrinsic fluorescence of KCl aqueous solution at room temperature and show that its intensity increases with the salt concentration. From the ab initio density functional theory (DFT) and time-dependent DFT modeling, we propose that the fluorescence emission could originate from the stiffening of the hydrogen bond network in the hydration shell of solvated ion-pairs that suppresses the fast nonradiative decay and allows the slower radiative channel to become a possible decay pathway. Because computations suggest that the fluorophores are the local ion-water structures present in the prenucleation phase, this band could be the signature of the incoming salt precipitation.
Articolo in rivista - Articolo scientifico
Hydrogen Bonding; Solutions; Spectrum Analysis; Sodium Chloride; Water
English
28-mar-2022
2022
126
13
2564
2572
open
Villa, A., Doglia, S., De Gioia, L., Natalello, A., Bertini, L. (2022). Fluorescence of KCl Aqueous Solution: A Possible Spectroscopic Signature of Nucleation. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 126(13), 2564-2572 [10.1021/acs.jpcb.2c01496].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/471283
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