Dipolar Correlations and the Dielectric Permittivity of Water

Sharma, Manu; Resta, Raffaele; Car, Roberto

doi:10.1103/physrevlett.98.247401

Cited by 172 publications

(194 citation statements)

References 29 publications

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“…The dipole moment of DMSO is 3.96 D [34] and larger than that of water molecules (1.85 D) [35]. The collective properties of water molecules are responsible for a much larger dielectric constant (~78) compared to that of DMSO (~48).…”

Section: The 1 L B Of Trp In Dmso Is a Results Of A Specific Solvent/smentioning

confidence: 99%

Site-directed circular dichroism of proteins: 1Lb bands of Trp resolve position-specific features in tear lipocalin

Gasymov

Abduragimov

Glasgow

2008

Analytical Biochemistry

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The absorption spectra of N-acetyl-L-tryptophanamide in various solvents were resolved into the sums of the 1 L a and 1 L b components. The relative intensities of the 0-0 transitions of the 1 L b bands correlate linearly with the solvent polarity values . A novel strategy, which utilizes a set of the experimental 1 L b bands, was employed to resolve the near-UV CD spectra of tryptophanyl residues. Resolved spectral parameters from the single-tryptophan mutants of tear lipocalin (TL), F99W and Y87W, corroborate the fluorescence as well as structural data of TL. Analysis of the 1 L b bands of the Trp CD spectra in proteins is a valuable tool to obtain the local features. The "DMSOlike" 1 L b band of Trp CD spectra may be used as a "fingerprint" to identify the tryptophanyl side chains in situations where the benzene rings of Trp have van der Waals interactions with the side chains of its nearest neighbor. In addition, the signs and intensities of the components hold information about the side-chain conformations and dynamics in proteins. Combined with Trp mutagenesis, this method we call site-directed circular dichroism is broadly applicable to various proteins to obtain the position-specific data.

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Section: The 1 L B Of Trp In Dmso Is a Results Of A Specific Solvent/smentioning

confidence: 99%

Site-directed circular dichroism of proteins: 1Lb bands of Trp resolve position-specific features in tear lipocalin

Gasymov

Abduragimov

Glasgow

2008

Analytical Biochemistry

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“…Moreover, the dielectric constant of liquid water is higher than that of all other polar liquids made of molecules with a comparable dipole moment, with several theoretical studies on this species being available in literature. 21 Finally, we present exploratory results for a much larger system, p-nitroaniline (C 6 H 4 NO 2 NH 2 or p -NA), a molecule known for its NLO properties and which has been theoretically and experimentally studied (ref 22 and references therein).…”

Section: E(f) ) E(0) -µFmentioning

confidence: 99%

Extrapolating to the One-Electron Basis Set Limit in Polarizability Calculations

Junqueira

Varandas

2008

J. Phys. Chem. A

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We report calculations of polarizabilities using total energies extrapolated to the complete basis set limit. A dual-level scheme has been employed, with the complete basis set limit of the correlation energy determined by the recently reported uniform singlet-and triplet-pair extrapolation method. The finite field approach has been employed, with tensors and averaged polarizabilities for the ground electronic states of H 2 , N 2 , CO, and H 2 O reported and compared with available experimental data in the literature. Exploratory results are also presented for C 6 H 4 NO 2 NH 2 .

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“…DOI: 10.1103/PhysRevLett.112.157802 PACS numbers: 61.20.Ja, 64.60.Q−, 64.70.F− Water is presumably the most used and the most studied substance among all the chemicals known to mankind. In particular, scientists have been attracted to the diverse structures of water clusters, liquid, and ice resulting from different orientations of hydrogen bonds and the associated phenomena [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. However, the liquid-vapor transition of water has been a subject of less intense investigation [15,16] because of difficulties in both experiment and computation due to the complicated metastable states separating the liquid and vapor phases.…”

mentioning

confidence: 99%

Limit of Metastability for Liquid and Vapor Phases of Water

et al. 2014

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We report the limits of superheating of water and supercooling of vapor from Monte Carlo simulations using microscopic models with configurational enthalpy as the order parameter. The superheating limit is well reproduced. The vapor is predicted to undergo spinodal decomposition at a temperature of T vap sp ¼ 46 AE 10°C (0°C ≪ T vap sp ≪ 100°C) under 1 atm. The water-water network begins to form at the supercooling limit of the vapor. Three-dimensional water-water and cavity-cavity unbroken networks are interwoven at critically superheated liquid water; if either network breaks, the metastable state changes to liquid or vapor. DOI: 10.1103/PhysRevLett.112.157802 PACS numbers: 61.20.Ja, 64.60.Q−, 64.70.F− Water is presumably the most used and the most studied substance among all the chemicals known to mankind. In particular, scientists have been attracted to the diverse structures of water clusters, liquid, and ice resulting from different orientations of hydrogen bonds and the associated phenomena [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. However, the liquid-vapor transition of water has been a subject of less intense investigation [15,16] because of difficulties in both experiment and computation due to the complicated metastable states separating the liquid and vapor phases. Given that everyday life experiences water evaporation and dew drops, it is ironic that these physical or chemical phenomena are not adequately understood. Simply, we are familiar with the generally learned fact that water boils at 100°C or 373 K at 1 atm. However, water can be superheated up to 603 K at 1 atm, and water vapor can be supercooled considerably below the boiling point [17][18][19][20][21] though the limit of supercooling is not known yet. This is due to unfavorable energetics at the formation of the liquid-vapor interface, which allow for the temporary existence of metastable states. According to the classical nucleation theory, the metastable states can be kept stable until stochastic fluctuations create the so-called critical cluster, which then grows spontaneously to make a new phase [22].However, these metastable states cease to exist when the liquid or vapor is brought to its stability limit, or spinodal. In this case, where the mother phase completely loses its thermodynamic stability, the phase transition takes place via spinodal decomposition [23]. It differs from classical nucleation in which the phase transition takes place at localized regions of space. Instead, the phase transition is considered to proceed by merging small embryos of daughter phase distributed uniformly over the space [24]. The lifetime of systems near the stability limit is too short to allow for accurate experimental determination of the spinodal. Hence, predicting the stability limit from a microscopic model of matter is of immense importance, given that there are a plethora of phenomena depending on the metastability throughout biology, meteorology, and industry [22].In this Letter, based on targeted sampling of metastable and unsta...

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Dipolar Correlations and the Dielectric Permittivity of Water

Cited by 172 publications

References 29 publications

Site-directed circular dichroism of proteins: 1Lb bands of Trp resolve position-specific features in tear lipocalin

Site-directed circular dichroism of proteins: 1Lb bands of Trp resolve position-specific features in tear lipocalin

Extrapolating to the One-Electron Basis Set Limit in Polarizability Calculations

Limit of Metastability for Liquid and Vapor Phases of Water

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