On the Existence of Free OH Groups in Liquid Water

Péron, J. J.; Bourdéron, C.; Sándorfy, C.

doi:10.1139/v71-652

Cited by 14 publications

(10 citation statements)

References 13 publications

(22 reference statements)

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“…It is then clear that the decrease in intensity of the first overtone does not necessarily imply a decrease in electrical anharmonicity as might have been thought (4). It is connected with the high value of p l , making a compensation possible between the terms containing p1 and p2 in eq.…”

Section: Introductionmentioning

confidence: 92%

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Model Calculations on the Influence of Mechanical and Electrical Anharmonicity on Infrared Intensities: Relation to Hydrogen Bonding

Paolo¹,

Bourdéron²,

Sándorfy³

1972

Can. J. Chem.

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The influence of mechanical and electrical anharmonicity on the intensity of X—H stretching vibrations is investigated by means of model calculations in relation to hydrogen bonding. It is found that while both kinds of anharmonicities have a significant effect on the intensity, they cannot explain the characteristic increase in intensity of the fundamental and the equally characteristic decrease in the intensity of the first overtone. It is shown that not only the first but both these phenomena are due to the large value of the first derivative of the dipole moment in hydrogen bonded systems. This is linked to the possibility that the effect of electrical anharmonicity (d2μ/dQ2) might be cancelled by a high value of (dμ/dQ)c in the expression of the overtone intensity.

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Section: Introductionmentioning

confidence: 92%

“…The influence of mechanical anharmonicity on the intensities has not been studied systematically. On the other hand electrical anharmonicity has been linked (3,4), to the surprising weakness of the first polymer overtone ( 5 ) .…”

Section: Introductionmentioning

confidence: 99%

Model Calculations on the Influence of Mechanical and Electrical Anharmonicity on Infrared Intensities: Relation to Hydrogen Bonding

Paolo¹,

Bourdéron²,

Sándorfy³

1972

Can. J. Chem.

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“…Measurement of the overtone absorption has some advantage over the fundamental absorption. Intensity of the overtone band is two orders of magnitude smaller than the fundamental OH stretching band, 30,31,[55][56][57][58] and the integrated intensity can be obtained with an optical pathlength of about 1 mm, which is in the range that can be controlled reasonably easily and accurately even at high temperatures and pressures. Furthermore, the effect of hydrogen bonding on the absorption intensity of the overtone band is much milder than that on the fundamental band.…”

Section: Introductionmentioning

confidence: 97%

“…Furthermore, the effect of hydrogen bonding on the absorption intensity of the overtone band is much milder than that on the fundamental band. 55,56 It is well established that the integrated intensity of the fundamental OH stretching band increases remarkably with increasing hydrogen bond strength. 59 For example, the molar absorption intensity of the water molecule increases by an order of magnitude from the gas to the liquid phase.…”

Section: Introductionmentioning

confidence: 99%

Near-infrared spectroscopic study of water at high temperatures and pressures

Jin

Ikawa

2003

The Journal of Chemical Physics

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Near-infrared absorption of the OH stretching overtone transition of water has been measured at temperatures and pressures in the ranges of 373–673 K and 20–400 bar, respectively. The absorption profile at 673 K and 400 bar retains a mark of rotational structure, indicating that an appreciable proportion of water molecules can rotate quite freely. The molar absorption intensity decreases linearly with increasing pressure in the low-pressure region. Enthalpy for dimerization has been estimated to be 15±3 kJ/mol from the temperature dependence of the slopes. Plots of the molar absorption intensity against molar concentration are observed to be located on a single curve irrespective of the temperature. This fact indicates that the ratio of hydrogen-bond formation is largely dependent on the molar density only. A good correlation between the molar absorption intensity and the first moments of the band has been found out; this will be useful in the study of aqueous mixtures

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“…[11,19] Roughly, the central frequencies of the sub-bands in the NIR spectra should be about twice those of the mid-infrared bands, as the expected anharmonicity correction of the OH stretching vibration is markedly smaller than the width of the two dominating sub-bands. [20] Allowing for some scatter in the literature data due to different fitting procedures and some dependence on the nature of the apolar component, the deconvolution of the NIR bands reported here is correspond well with results for a variety of AOT-based reverse micellar systems in the mid-infrared.…”

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confidence: 99%

Small‐Angle X‐Ray Scattering and Near‐Infrared Vibrational Spectroscopy of Water Confined in Aerosol‐OT Reverse Micelles

et al. 2008

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The state of water confined in Aerosol-OT-hydrocarbon-water reverse micelles with cyclohexane, n-pentane, n-octane, and n-dodecane as apolar solvents is investigated by small-angle X-ray scattering and near-infrared vibrational spectroscopy of the first overtone of the OH stretching mode of water. The experiments focus on water/AOT molecular ratios W(0)=2-20, where water is strongly affected by the confinement and surface-water interactions. The pair-distance distribution functions derived from the small-angle scattering patterns allows a detailed characterization of the topology of these systems, and they indicate deviations from monodisperse, spherical water pools for some of these hydrocarbon systems. In contrast to a common assumption, the pool size does not scale linearly with W(0) in going from dry reverse micelles (W(0)-->0) to essentially bulk-like water (W(0)>20). The first overtone of the OH-stretching vibration exhibits highly structured spectra, which reveal significant changes in the hydrogen bonding environment upon confinement. The spectra are rationalized by a core/shell model developed by Fayer and co-workers. This model subdivides water into core water in the interior of the micelle and shell water close to the interface. Core water is modelled by the properties of bulk water, while the properties of shell water are taken to be those of water at W(0)=2. The model allows the representation of the spectra at any hydration level as a linear combination of the spectra of core and shell water. Different approaches are critically reviewed and discussed as well.

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On the Existence of Free OH Groups in Liquid Water

Cited by 14 publications

References 13 publications

Model Calculations on the Influence of Mechanical and Electrical Anharmonicity on Infrared Intensities: Relation to Hydrogen Bonding

Model Calculations on the Influence of Mechanical and Electrical Anharmonicity on Infrared Intensities: Relation to Hydrogen Bonding

Near-infrared spectroscopic study of water at high temperatures and pressures

Small‐Angle X‐Ray Scattering and Near‐Infrared Vibrational Spectroscopy of Water Confined in Aerosol‐OT Reverse Micelles

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