Local Electric Fields in Aqueous Electrolytes
نویسندگان
چکیده
Vibrational Stark shifts were explored in aqueous solutions of organic molecules with carbonyl- and nitrile-containing constituents. In many cases, the vibrational resonances from these moieties shifted toward lower frequency as salt was introduced into solution. This is contrast to blue-shift that would be expected based upon Onsager's reaction field theory. Salts containing well-hydrated cations like Mg2+ or Li+ led most pronounced shift for carbonyl group, while poorly hydrated Cs+ had greatest impact on nitriles. Moreover, salts I- gave rise larger than those Cl-. Molecular dynamics simulations indicated anions both accumulate around probe an ion- probe-dependent manner. An electric generated by ion pair, which pointed cation anion through chromophore. resulted solvent-shared binding ions probes, consistent their positions Hofmeister series. The anti-Onsager occur spectroscopy fluorescence measurements.
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ژورنال
عنوان ژورنال: Journal of Physical Chemistry B
سال: 2021
ISSN: ['1520-6106', '1520-5207']
DOI: https://doi.org/10.1021/acs.jpcb.1c03257