Effects of stearyl alcohol monolayer on the structure, dynamics and vibrational sum frequency generation spectroscopy of interfacial water

Das, Banshi; Chandra, Amalendu

doi:10.1039/d1cp04944e

Cited by 7 publications

(12 citation statements)

References 122 publications

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“…Recent work of Paesani and co-workers, who have calculated VSFG spectra computationally for different alcohol monolayers, has demonstrated the presence of various kinds of water molecules at the interface. Similar study on an alcohol–water interface is also reported recently by Das and Chandra . In another study, NaCl distribution at the alcohol–water interface has been examined through MD simulations.…”

Section: Introductionsupporting

confidence: 74%

“…Similar study on an alcohol−water interface is also reported recently by Das and Chandra. 69 In another study, NaCl distribution at the alcohol− water interface has been examined 63 through MD simulations. Yang et al 65 have studied the hexane−water interface using ab initio simulations as well as VSFG spectroscopy and analyzed the stability of OH − ions in hydrophobic monolayer−water interfacial region.…”

Section: Introductionmentioning

confidence: 99%

“…In fact, according to the classical theory of continuum electrostatics and point charge assumptions, ions should be pushed away from the interface into the bulk due to image charge repulsion across the interface. , Because such air–water and oil–water interfaces are ubiquitous in many natural and technological processes, a large body of both experimental and computational studies have been devoted − over the years to explore the structure/orientation of water at free liquid–vapor interfaces − and adsorption and distribution of self-ions (OH – and H 3 O + ions) of water at the air–water interface. − …”

Section: Introductionmentioning

confidence: 99%

“…Only a few studies have been reported on such alcohol–water interfaces. Alcohol–water monolayer has also been shown to induce ice nucleation. , In recent simulation studies, , water structure/orientation at the long-chain alcohol–water interfaces has been studied by computationally calculating the VSFG spectra. Recent work of Paesani and co-workers, who have calculated VSFG spectra computationally for different alcohol monolayers, has demonstrated the presence of various kinds of water molecules at the interface.…”

Section: Introductionmentioning

confidence: 99%

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On the Propensity of Excess Hydroxide Ions at the Alcohol Monolayer–Water Interface

2023

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Atomistic molecular dynamics simulations have been employed to study the self-ion (H + and OH − ) distribution at the interface between long-chain C 16 −OH alcohol (cetyl alcohol) monolayer and water. It is well known that the free air−water interface is acidic due to accumulation of the hydronium (H 3 O + ) ions at the interface. In the present study, we have observed that contrary to the air−water interface, at the long-chain alcohol monolayer−water interface, it is the hydroxide (OH − ) ion, not the hydronium ion (H 3 O + ) that gets accumulated. By calculating the potential of mean forces, it is confirmed that there is extra stabilization for the OH − ions at the interface relative to the bulk, but no such stabilization is observed for the H 3 O + ions. By analyzing the interaction of the self-ions with other constituents in the medium, it is clearly shown that the favorable interaction of the OH − ions with the alcoholic −OH groups stabilizes this ion at the interface. By calculating coordination numbers of the self-ions it is observed that around 50% water neighbors are substituted by alcoholic −OH in case of the hydroxide ion at the interface, whereas in the case of hydronium ions, only 15% water neighbors are substituted by the alcoholic −OH. The most interesting observation about the local structure and H-bonding pattern is that the hydroxide ion acts solely as the H-bond acceptor, but the hydronium ion acts only as the H-bond donor.

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Section: Introductionsupporting

confidence: 74%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the Propensity of Excess Hydroxide Ions at the Alcohol Monolayer–Water Interface

2023

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“…Recently, Das et al investigated SFVS of alcohols on water at the gas/liquid interfaces using classical and first principle simulations. 89,90 Herein, we compare their method with ours:…”

Section: Resultsmentioning

confidence: 99%

Sum-frequency vibrational spectroscopy of methanol at interfaces due to Fermi resonance

Zheng

Wei

2022

Phys. Chem. Chem. Phys.

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Vibrational Sum Frequency Generation Spectra of Water‐Vapor Interfaces Covered by Alcohols: Effects of Surface Coverage and Coupling between Oscillators

Das

Chandra

2023

ChemPhysChem

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The present study deals with the effects of varying coverage of water surface by alcohols on the vibrational sum frequency generation (VSFG) spectrum of interfacial water. We have considered two different alcohols: Tertiary butyl alcohol (TBA) whose alkyl part is fully branched and stearyl alcohol (STA) which has a long linear alkyl chain with larger hydrophobic surface area than that of TBA. With increase of the alcohol concentration, the hydrogen bonded OH stretch region of the VSFG spectrum is found to change following a regular trend for the STA‐water system, whereas non‐monotonic variation of the VSFG spectrum is observed for the TBA‐water system which can be correlated with the presence of very different interactions of TBA molecules at different concentrations. On increasing the concentration of TBA, the hydrophobic groups get more tilted towards the water phase and significant hydrophobic interactions are introduced at higher concentrations. Whereas, for STA, there is a gradual increase in the hydrophilic interaction. Because of stacking interactions between the long chain alkyl groups, the hydrophobic parts stay outward from the water phase at higher concentrations and a regular change in the VSFG spectrum is observed. We have also presented a computationally efficient scheme to calculate the VSFG spectrum of interfacial systems for coupled oscillators which is expected to be beneficial for the treatment of coupling where the interfacial system size is inherently large.

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Effects of stearyl alcohol monolayer on the structure, dynamics and vibrational sum frequency generation spectroscopy of interfacial water

Abstract: The structure, dynamics and vibrational spectroscopy of water surface covered by a monolayer of stearyl alcohol (STA) are investigated by means of molecular dynamics simulations and vibrational sum frequency generation...

Cited by 7 publications

References 122 publications

On the Propensity of Excess Hydroxide Ions at the Alcohol Monolayer–Water Interface

On the Propensity of Excess Hydroxide Ions at the Alcohol Monolayer–Water Interface

Sum-frequency vibrational spectroscopy of methanol at interfaces due to Fermi resonance

Vibrational Sum Frequency Generation Spectra of Water‐Vapor Interfaces Covered by Alcohols: Effects of Surface Coverage and Coupling between Oscillators

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