Stern and Diffuse Layer Interactions during Ionic Strength Cycling

doi:10.1021/acs.jpcc.1c04836

Stern and Diffuse Layer Interactions during Ionic Strength Cycling

2021-08-05

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DOI：10.1021/acs.jpcc.1c04836

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Second harmonic generation amplitude and phase measurements are acquired in real time from fused silica:water interfaces that are subjected to ionic strength transitions conducted at pH 5.8. In conjunction with atomistic modeling, we identify correlations between structure in the Stern layer, encoded in the total second-order nonlinear susceptibility, chi((2))(tot) and in the diffuse layer, encoded in the product of chi((2))(tot) and the total interfacial potential, Phi(0)(tot). The chi((2))(tot):Phi(0)(tot) correlation plots indicate that the dynamics in the Stern and diffuse layers are decoupled from one another under some conditions (large change in ionic strength), while they change in lockstep under others (smaller change in ionic strength) as the ionic strength in the aqueous bulk solution varies. The quantitative structural and electrostatic information obtained also informs on the molecular origin of hysteresis in ionic strength cycling over fused silica. Atomistic simulations suggest a prominent role of contact ion pairs (as opposed to solvent-separated ion pairs) in the Stern layer. Those simulations also indicate that net water alignment is limited to the first 2 nm from the interface, even at 0 M ionic strength, highlighting water's polarization as an important contributor to nonlinear optical signal generation.

Keywords:

SUM-FREQUENCY GENERATION

INTERFACIAL WATER-STRUCTURE

ELECTRICAL DOUBLE-LAYER

GOUY-CHAPMAN MODEL

VIBRATIONAL SPECTROSCOPY

2ND-HARMONIC GENERATION

CHARGED INTERFACES

MOLECULAR-DYNAMICS

BULK CONTRIBUTIONS

SURFACE

Stern and Diffuse Layer Interactions during Ionic Strength Cycling

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