2024/01/11 by Akira Ōnuki, Onuki, Akira · 1 citation
Computer Science · Neuroscience · Physics and Astronomy · #FOS: Physical sciences #Photoreceptor and optogenetics research #Quantum Information and Cryptography #Soft Condensed Matter (cond-mat.soft) #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.2401.05825
openalex publication_date 2024/01/11 · openalex created_date 2024/01/13 · openalex updated_date 2026/07/28
We investigate electric-field effects in dilute electrolytes with nonlinear polarization. As a first example of such systems, we add a dipolar component with a relatively large dipole moment μ0 to an aqueous electrolyte. As a second example, the solvent itself exhibits nonlinear polarization near charged objects. For such systems, we present a Ginzburg-Landau free energy and introduce field-dependent chemical potentials, entropy density, and stress tensor, which satisfy general thermodynamic relations. In the first example, the dipoles accumulate in high-field regions, as predicted by Abrashikin \it et al.[Phys.Rev.Lett. \bf 99, 077801 (2007)]. Finally, we consider the case, where Bjerrum ion pairs form a dipolar component with nonlinear polarization. The Bjerrum dipoles accumulate in high-field regions, while field-induced dissociation was predicted by Onsager [J. Chem. Phys.\bf 2, 599 (1934)]. We present an expression for the field-dependent association constant K(E), which depends on the field strength nonmonotonically.