Manifestation of cluster excitations in dielectric properties of water vapor and liquid water as well as their heat capacity

Makhlaichuk, Viktor N.; Malomuzh, N. P.

doi:10.1016/j.molliq.2018.01.018

Cited by 7 publications

(3 citation statements)

References 27 publications

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“…This circumstance radically distinguishes their origin from that of their vapors at the coexistence curves. It is important to note that the effective polarization of water demonstrates the same features in its behavior [25,26]. In the case of water, such a behavior is associated with the thermal excitation of clusters formed in water and with strong orientational correlations that only result in the appearance of fluctuation dipole moments in clusters.…”

Section: Static Dielectric Permittivities Of Alcohols From the Methanmentioning

confidence: 91%

Extraordinary Properties of Alcohols from the Homologous Series of Methanol

2020

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Non-trivial properties of thermodynamic quantities such as the density, the critical and triple point temperatures, and their ratio, as well as the optical and dielectric properties, have been analyzed for primary alcohols from the methanol series. The aim is to reveal relationships among their values measured at the same temperatures for alcohols with different ordinal numbers m’s in the methanol series. It is shown that the non-monotonic character of the temperature dependences of alcohol densities is associated with methanol rather than ethanol, as may seem at first glance. The critical temperature of methanol also deviates from the quasilinear dependence of the critical alcohol temperatures on m. With the growing m, the ratio between the critical and triple-point temperatures for alcohols is shown to tend to the corresponding value for water. Simple linear dependences of the electronic and effective static polarizabilities of alcohol molecules on m are established. The transverse and longitudinal components of the polarizability tensor for alcohol molecules are found. The dipole moments of the closest neighbor molecules in the alcohols are proved to anticorrelate, i.e. to orient in opposite directions.

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Section: Static Dielectric Permittivities Of Alcohols From the Methanmentioning

confidence: 91%

Extraordinary Properties of Alcohols from the Homologous Series of Methanol

2020

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“…In general, the heat capacity of liquids reflects the combination of (translational, rotational and vibrational) motion and intermolecular interactions [205][206][207][208][209][210][211][212]. Moreover, the description for water is further complicated due to its extensive hydrogen bonding [213][214][215][216][217][218][219][220][221][222]. A number of different (and not entirely consistent) explanations for its 'anomalously' high heat capacity have been proposed, based on contributions due to water clusters [213][214][215]219,220]; the distribution of rotational and vibrational energy levels [216][217][218]; temperature-driven breaking of H-bonds [219] and vibrations in the Hbonded network [220].…”

Section: Discussionmentioning

confidence: 99%

“…Moreover, the description for water is further complicated due to its extensive hydrogen bonding [213][214][215][216][217][218][219][220][221][222]. A number of different (and not entirely consistent) explanations for its 'anomalously' high heat capacity have been proposed, based on contributions due to water clusters [213][214][215]219,220]; the distribution of rotational and vibrational energy levels [216][217][218]; temperature-driven breaking of H-bonds [219] and vibrations in the Hbonded network [220]. In the absence of a clear explanation applicable to 'free' water, however, a precise explanation for the decrease in heat capacity through interaction with fibroin (or other solutes) is somewhat speculative.…”

Section: Discussionmentioning

confidence: 99%

Seeking Solvation: Exploring the Role of Protein Hydration in Silk Gelation

Laity

Holland

2022

Molecules

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The mechanism by which arthropods (e.g., spiders and many insects) can produce silk fibres from an aqueous protein (fibroin) solution has remained elusive, despite much scientific investigation. In this work, we used several techniques to explore the role of a hydration shell bound to the fibroin in native silk feedstock (NSF) from Bombyx mori silkworms. Small angle X-ray and dynamic light scattering (SAXS and DLS) revealed a coil size (radius of gyration or hydrodynamic radius) around 12 nm, providing considerable scope for hydration. Aggregation in dilute aqueous solution was observed above 65 °C, matching the gelation temperature of more concentrated solutions and suggesting that the strength of interaction with the solvent (i.e., water) was the dominant factor. Infrared (IR) spectroscopy indicated decreasing hydration as the temperature was raised, with similar changes in hydration following gelation by freezing or heating. It was found that the solubility of fibroin in water or aqueous salt solutions could be described well by a relatively simple thermodynamic model for the stability of the protein hydration shell, which suggests that the affected water is enthalpically favoured but entropically penalised, due to its reduced (vibrational or translational) dynamics. Moreover, while the majority of this investigation used fibroin from B. mori, comparisons with published work on silk proteins from other silkworms and spiders, globular proteins and peptide model systems suggest that our findings may be of much wider significance.

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pH and H-bonding energy for pure water

Khorolskyi

Malomuzh²

2023

Chemical Physics Letters

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Manifestation of cluster excitations in dielectric properties of water vapor and liquid water as well as their heat capacity

Cited by 7 publications

References 27 publications

Extraordinary Properties of Alcohols from the Homologous Series of Methanol

Extraordinary Properties of Alcohols from the Homologous Series of Methanol

Seeking Solvation: Exploring the Role of Protein Hydration in Silk Gelation

pH and H-bonding energy for pure water

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