Local and Global Effects of Dissolved Sodium Chloride on the Structure of Water

Journal Article · Tue Mar 14 04:00:00 EDT 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b00239· OSTI ID:1489265

Gaiduk, Alex P. ^[1]; Galli, Giulia ^[2]

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1. Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, United States
2. Institute for Molecular Engineering, The University of Chicago, Chicago, Illinois 60637, United States; Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States

Determining how the structure of water is modified by the presence of salts is instrumental to understanding the solvation of biomolecules and, in general, the role played by salts in biochemical processes. However, the extent of hydrogen bonding disruption induced by salts remains controversial. We performed extensive first-principles simulations of solutions of a simple salt (NaCl) and found that, while the cation does not significantly change the structure of water beyond the first solvation shell, the anion has a further reaching effect, modifying the hydrogen-bond network even outside its second solvation shell. We found that a distinctive fingerprint of hydrogen bonding modification is the change in polarizability of water molecules. Molecular dipole moments are instead insensitive probes of long-range modifications induced by Na⁺ and Cl^- ions. Though noticeable, the long-range effect of Cl^- is expected to be too weak to affect solubility of large biomolecules.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1489265
• Journal Information: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 7 Vol. 8; ISSN 1948-7185
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English