Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Khaliullin, Rustam Z.; Kühne, Thomas D.

doi:10.1039/c3cp51039e

Cited by 62 publications

(90 citation statements)

References 206 publications

(460 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The remaining frequencies above 3000 cm −1 are the OH stretching modes . However, at variance to bulk water, we observe a generally larger splitting between the symmetric and asymmetric stretching modes, which immediately suggests that the asymmetry of the hydrogen‐bond network is more pronounced due to the presence of the solute . In the case of the hydrophobic cyclohexane molecule, the effect is even more pronounced.…”

Section: Resultsmentioning

confidence: 67%

Efficient “On‐the‐Fly” calculation of Raman Spectra fromAb‐Initiomolecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

Partovi–Azar¹,

Kühne

2015

J Comput Chem

Self Cite

View full text Add to dashboard Cite

We present a novel computational method to accurately calculate Raman spectra from first principles. Together with an extension of the second-generation Car-Parrinello method of Kühne et al. (Phys. Rev. Lett. 2007, 98, 066401) to propagate maximally localized Wannier functions together with the nuclei, a speed-up of one order of magnitude can be observed. This scheme thus allows to routinely calculate finite-temperature Raman spectra "on-the-fly" by means of ab-initio molecular dynamics simulations. To demonstrate the predictive power of this approach we investigate the effect of hydrophobic and hydrophilic solutes in water solution on the infrared and Raman spectra.

show abstract

Section: Resultsmentioning

confidence: 67%

Efficient “On‐the‐Fly” calculation of Raman Spectra fromAb‐Initiomolecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

Partovi–Azar¹,

Kühne

2015

J Comput Chem

Self Cite

View full text Add to dashboard Cite

show abstract

“…approaches 19,59 and the linear-scaling EDA of Phipps et al 60 ) and their ability to treat many-fragment systems, 61 they are instrumental in the continuing effort to better understand liquid water and ice, [62][63][64] cooperative effects, 25,[65][66][67][68] and other interactions in solution. 69,70 Moreover, they treat both inter-and intramolecular 18,19,43,71 (including through-bond) interactions on equal footing (including through bond) and, thus, capably describe phenomena that are of a mixed or non-covalent nature, e.g., dative bonds, 27,72,73 as well as chemisorption and physisorption processes 221,222 (through a "periodic EDA" by Tonner et al 223 ).…”

Section: Figmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

105

102

View full text Add to dashboard Cite

Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

show abstract

“…The broader peak actually indicates different binding states of water molecules contributing to the overall signal. Two major contributions typically discussed in the literature are the so‐called loosely bound ‘liquid’‐like water and the firmly bound ordered ‘ice’‐like water species . In the context of the presented data, the long shoulder of the OH‐related signal toward lower wave numbers indicates the presence of highly ordered ice‐like water species.…”

mentioning

confidence: 63%

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

Torun

Giner

Grundmeier

et al. 2016

Surface & Interface Analysis

View full text Add to dashboard Cite

In situ photoelastic-modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the crosslinked film. This high water activity at the interface leads to a reversible wet de-adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S-Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross-linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.Keywords: interfacial stability; photoelastic-modulated Fourier transform infrared reflection absorption spectroscopy (PM-IRRAS); organofunctional monolayer films; zinc oxide; organosilane Thin organic films play an important role in microsensors, electronics and optical devices and offer wide possibilities in tuning surface and interface properties for the development of protective coatings and biocompatible materials. [1][2][3][4][5][6][7] Organosilanols are a class of functional molecules that are able to react with organic and inorganic surfaces through surface hydroxyl groups to form an interface dominated by van der Waals and hydrogen bonding interactions that could be converted to covalent bonds via hydrolysis reactions, usually achieved by means of a thermal treatment. [1,8,9] Even though the exact mechanism of the film formation is still not fully understood, the consensus in the literature points to a stepwise evolution of the cross-linked siloxane network via the hydrolysis of halogen or alkoxy groups to silanols in contact with water, which can then further react to form the Si-O-Si and Si-O metal bonds. [10,11] While the Si-O-Si bond formation can be easily proven, the covalent bond formation to metal and oxide-covered metal substrates especially in the presence of water is questionable.In a recent study, Naik and coworkers have investigated the effect of the degree of polymerization on the film formation of alkylsilane monolayers on silica surfaces and have concluded that the inherent stress caused by the mismatch of alkyl-chain van der Waals radius and Si-O-Si bond distance results in the adsorption of structures resembling snow moguls or closely packed umbrellas.[11] Organothiols and organophosphonic acids, which can form stable interfaces on zinc oxide surfaces, have been investigated as adhesion promoters on various metal-metal oxide surfaces, as insulating layers on circuit materials, as well as possible linkers for sensor and biosensor applications. [4,5,7,12,13] In most of the aforementioned application fields, the stability of the thin functional films is strongly dependent on the strength of the interfacial interactions...

show abstract

Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies

Cited by 62 publications

References 206 publications

Efficient “On‐the‐Fly” calculation of Raman Spectra fromAb‐Initiomolecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

Efficient “On‐the‐Fly” calculation of Raman Spectra fromAb‐Initiomolecular dynamics: Application to hydrophobic/hydrophilic solutes in bulk water

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

Contact Info

Product

Resources

About