Asymmetric response of interfacial water to applied electric fields

Montenegro, Angelo; Dutta, Chayan; Mammetkuliev, Muhammet; Shi, Haotian; Hou, Bingya; Bhattacharyya, Dhritiman; Zhao, Bofan; Cronin, Stephen B.; Benderskii, Alexander V.

doi:10.1038/s41586-021-03504-4

Cited by 109 publications

(95 citation statements)

References 40 publications

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“…6 The apparently universal negative CME in metal-water interfaces is attributed to the oxygen end of water facing the electrode at the PZC, requiring a negative electrode charge to counter this preferential orientation and increase the entropy. 7 This asymmetry of interfacial water also agrees with recent spectroscopic evidence 15 and molecular dynamics (MD) studies on interfacial water dynamics 16 , prompting the question whether the inner layer capacitance is similarly asymmetric.…”

Section: Introductionsupporting

confidence: 77%

Interfacial water asymmetry at ideal electrochemical interfaces

Shandilya,

Schwarz,

Sundararaman

2022

Preprint

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Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements, and the thermodynamics of the inner layer with potential of maximum entropy (PME) measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of ab initio MD (AIMD). Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory (DFT) to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that, while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between -3.7 µC/cm 2 and -3.3 µC/cm 2 , regardless of details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of −6.4 ± 0.7 µC/cm 2 , in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.

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Section: Introductionsupporting

confidence: 77%

Interfacial water asymmetry at ideal electrochemical interfaces

Shandilya,

Schwarz,

Sundararaman

2022

Preprint

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“…It should be noted that the net potential drop between the air–water interface and the monolayer surface is between 0.4 and 1.0 V. It is important to note that in the presence of interfacial potential, absorptive-dispersive mixing is crucial and controls the spectral line shapes of the VSFG spectra. Different groups have tried to quantify the χ (3) contribution to the total VSFG intensity and concluded that it is non-negligible in such systems because of the breaking of centro-symmetry at the interfaces and extended influence of the charged interfaces into the diffuse and bulk layers. − The χ (3) contribution to the VSFG spectrum mainly emanates from the molecules in the diffuse layer. The potential contribution from the diffuse layers onto the interface can be extracted by applying the parallel capacitor principle, i.e ., by fitting a linear relation between the potential and the distance from the interface in the diffuse layer region and then extrapolating the same up to the interface.…”

Section: Resultsmentioning

confidence: 99%

Spectral Response of Interfacial Water at Different Lipid Monolayer Interfaces upon Interaction with Charged Gold Nanoparticles

2021

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Understanding the interactions of nanoparticles with cell membranes is crucial for designing materials for biomedical applications. In this paper, through the combination of vibrational sum frequency generation (VSFG) and molecular dynamics simulation techniques, the spectral responses of the interfacial water molecules due to interaction of anionic gold nanoparticles (AGNPs) and cationic gold nanoparticles (CGNPs) with three differently charged model cell membranes, namely, 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG, negatively charged), 1,2-dipalmitoyl-3-trimethylammonium-propane (DPTAP, positively charged), and zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC, neutral), have been investigated. The interfacial water intensity at the DPPG–water interface decreases abruptly in the presence of CGNPs because of the significant change in Stern layer configuration, whereas it does not show any noticeable change in the presence of AGNPs, resulting in an unperturbed stern layer configuration. However, in the case of DPTAP and DPPC interfaces, the Stern layer is significantly perturbed in the presence of both the charged GNPs, resulting in a substantial change in the interfacial water intensity. This is attributed to the change in orientation and structure of interfacial water molecules in the presence of both charged GNPs. These results provide valuable insights into the solvation structure and dynamics of water molecules to exploit for designing and optimizing the delivery system for biomedical applications.

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“…The exact origin of the two peaks is still being investigated (Sovago et al, 2008;Myalitsin et al, 2016), but it is generally agreed that the lower the OH stretching frequency is, the stronger, and/or more ordered, H-bonding environment the corresponding moieties sense. On the bulk-SiO 2 /H 2 O interfaces, the 3,200 cm −1 mode (assigned to the topmost water layer (Urashima et al, 2018)) was found to grow more rapidly than the 3,400 cm −1 one (H-bonded to bulklike water molecules (Montenegro et al, 2021)) at increasing pH, which suggested a more ordered water structure near the more negatively charged surface. In contrast, in our case, when the SiO 2 surface bound charge evolved from positive to negative, the 3,400 cm −1 mode appeared to increase more rapidly.…”

Section: Sfvs In H 2 Omentioning

confidence: 94%

“…The rich phenomena and functionalities of oxide/water interfaces are largely based on their interfacial charging states and properties of EDLs (Brown, 2001;Putnis, 2014;Covert and Hore, 2016;Ohno et al, 2016;Schaefer et al, 2018). For example, the water electric dipole moment can be aligned by the electrostatic field in EDL and affect the interfacial chemistry (Brown, 2001;Nihonyanagi et al, 2004;Aragones et al, 2011;Saitta et al, 2012;Brown et al, 2016;Montenegro et al, 2021). In the case of ice, such field alignment could give rise to a ferroelectric state of highly oriented water molecules, which was readily probed using the surfacesensitive sum-frequency vibrational spectroscopy (SFVS) (Miranda et al, 1998;Verdaguer et al, 2006;Anim-Danso et al, 2016).…”

Section: Introductionmentioning

confidence: 99%

Gate Alignment of Liquid Water Molecules in Electric Double Layer

Duan

Lin

et al. 2021

Front. Chem.

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The behavior of liquid water molecules near an electrified interface is important to many disciplines of science and engineering. In this study, we applied an external gate potential to the silica/water interface via an electrolyte-insulator-semiconductor (EIS) junction to control the surface charging state. Without varying the ionic composition in water, the electrical gating allowed an efficient tuning of the interfacial charge density and field. Using the sum-frequency vibrational spectroscopy, we found a drastic enhancement of interfacial OH vibrational signals at high potential in weakly acidic water, which exceeded that from conventional bulk-silica/water interfaces even in strong basic solutions. Analysis of the spectra indicated that it was due to the alignment of liquid water molecules through the electric double layer, where the screening was weak because of the low ion density. Such a combination of strong field and weak screening demonstrates the unique tuning capability of the EIS scheme, and would allow us to investigate a wealth of phenomena at charged oxide/water interfaces.

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Asymmetric response of interfacial water to applied electric fields

Cited by 109 publications

References 40 publications

Interfacial water asymmetry at ideal electrochemical interfaces

Interfacial water asymmetry at ideal electrochemical interfaces

Spectral Response of Interfacial Water at Different Lipid Monolayer Interfaces upon Interaction with Charged Gold Nanoparticles

Gate Alignment of Liquid Water Molecules in Electric Double Layer

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