title: Anomalous microscopic dielectric response of dipolar solvents and water.
abstract: This paper reports measurements of static microscopic dielectric response of several dipolar solvents to charge redistribution in a fluorescent probe. Contrary to recent predictions of dielectric theories and computer simulations of bulk liquids, the observed dielectric response of most solvents conforms to the macroscopic continuum description even at atomic distances, as if these solvents had no spatial intermolecular structure. Such conformance is observed for several probes when the contribution of specific probe-solvent interactions to the response is negligible. However, water, formamide, and glycerol exhibit anomalous responses even though such a probe is used. We discuss a possible reason for the macroscopic-like behavior and a connection between the anomaly and fluctuating structures formed by anomalous solvents near the hydrophobic surface of the probe.
authors.affiliation: National Institute of Child Health and Human Development, National Institutes of Health, Department of Health and Human Services, Bldg. 9, Rm. 1E125, Bethesda, Maryland 20892-0924, USA. mertze@mail.nih.gov
authors.forename: Edward L
authors.initials: EL
authors.lastname: Mertz
mesh_terms: D004583:Electrons; D008853:Microscopy; D008958:Models, Molecular; D015394:Molecular Structure; D011312:Pressure; D012997:Solvents / Q000737:chemistry*; D013696:Temperature; D014867:Water / Q000737:chemistry*
chemical_list: D012997:Solvents; D014867:Water