title: Electrolytes induce long-range orientational order and free energy changes in the H-bond network of bulk water.
abstract: Electrolytes interact with water in many ways: changing dipole orientation, inducing charge transfer, and distorting the hydrogen-bond network in the bulk and at interfaces. Numerous experiments and computations have detected short-range perturbations that extend up to three hydration shells around individual ions. We report a multiscale investigation of the bulk and surface of aqueous electrolyte solutions that extends from the atomic scale (using atomistic modeling) to nanoscopic length scales (using bulk and interfacial femtosecond second harmonic measurements) to the macroscopic scale (using surface tension experiments). Electrolytes induce orientational order at concentrations starting at 10 μM that causes nonspecific changes in the surface tension of dilute electrolyte solutions. Aside from ion-dipole interactions, collective hydrogen-bond interactions are crucial and explain the observed difference of a factor of 6 between light water and heavy water.
authors.affiliation: Laboratory for fundamental BioPhotonics, Institutes of Bioengineering and Materials Science and Engineering, School of Engineering, and Lausanne Centre for Ultrafast Science, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Yixing
authors.initials: Y
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Pennsylvania State University, University Park, PA 16802, USA.
authors.forename: Halil I
authors.initials: HI
authors.lastname: Okur
authors.affiliation: Laboratory for fundamental BioPhotonics, Institutes of Bioengineering and Materials Science and Engineering, School of Engineering, and Lausanne Centre for Ultrafast Science, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Nikolaos
authors.initials: N
authors.lastname: Gomopoulos
authors.affiliation: Laboratory for fundamental BioPhotonics, Institutes of Bioengineering and Materials Science and Engineering, School of Engineering, and Lausanne Centre for Ultrafast Science, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Carlos
authors.identifier: 0000-0002-6533-5835
authors.initials: C
authors.lastname: Macias-Romero
authors.affiliation: Department of Chemistry, Pennsylvania State University, University Park, PA 16802, USA.; Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, PA 16802, USA.
authors.forename: Paul S
authors.initials: PS
authors.lastname: Cremer
authors.affiliation: Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USA.
authors.forename: Poul B
authors.initials: PB
authors.lastname: Petersen
authors.affiliation: Laboratory for fundamental BioPhotonics, Institutes of Bioengineering and Materials Science and Engineering, School of Engineering, and Lausanne Centre for Ultrafast Science, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.; Laboratory of Computational Science and Modeling, Institute of Materials Science and Engineering, School of Engineering, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Tocci
authors.affiliation: Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, UK.
authors.forename: David M
authors.initials: DM
authors.lastname: Wilkins
authors.affiliation: Laboratory of Computational Science and Modeling, Institute of Materials Science and Engineering, School of Engineering, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Chungwen
authors.initials: C
authors.lastname: Liang
authors.affiliation: Laboratory of Computational Science and Modeling, Institute of Materials Science and Engineering, School of Engineering, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Michele
authors.initials: M
authors.lastname: Ceriotti
authors.affiliation: Laboratory for fundamental BioPhotonics, Institutes of Bioengineering and Materials Science and Engineering, School of Engineering, and Lausanne Centre for Ultrafast Science, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Sylvie
authors.initials: S
authors.lastname: Roke
mesh_terms: D004573:Electrolytes / Q000737:chemistry*; D006860:Hydrogen Bonding; D036103:Nanotechnology; D013499:Surface Properties; D014867:Water / Q000737:chemistry*
chemical_list: D004573:Electrolytes; D014867:Water
keywords: Water; electrolytes; hydrogen bonding; molecular dynamics; nonlinear light scattering; nuclear quantum effects; second harmonic generation; surface tension.