Intramolecular Interactions in the Water Molecule: The Stretch–Stretch Interaction Force Constant of Water Molecules in Hydrogen-Bonded Systems

Fifer, Robert A.; Schiffer, J.

doi:10.1063/1.1673355

Cited by 35 publications

(8 citation statements)

References 22 publications

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“…This difference may be due to a smaller v,-v, splitting in the crystal than in the vapor or to the vibrations that contribute to the v, in-phase and out-ofphase bands not having near neighbors moving precisely in phase or out of phase respectively, or to a combination of both. Fifer and Schiffer (60) have shown that the v,-v, splitting of water molecules in several metal chloride hydrates is significantly smaller than in the vapor. While the hydrogen bonding in these salts may not be exactly comparable to that in ice I, the observation is consistent with the proposed assignment of ice I.…”

Section: Disordered Ice Icmentioning

confidence: 99%

A detailed assignment of the O–H stretching bands of ice I

Whalley¹

1977

Can. J. Chem.

197

171

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E. WHALLEY. Can. J. Chem. 55,3429 (1977). A detailed assignment of the infrared and Raman 0-H stretching bands of disordered ice Ih and Ic is proposed. It is based on the assumptions that the spectra of disordered ice Ic are closely related to those of ordered ice Ic, and that the spectra of the as yet unrealized ordered ice Ic can be predicted from the spectra of ice VIII. The supposed similarity between the spectra of ordered and disordered ice Ic is justified by the observed similarity of the spectra of ice VIII and VII, which are respectively ordered and disordered forms of the same structure and are closely related to ordered and disordered ice Ic. The assignment takes into account the intermolecular coupling, which is particularly strong for the v, vibrations but weak for the v,, and the TO-LO splitting, particularly of the v, vibrations, which is shown to be required by the high infrared intensity. The infrared and Raman bands of amorphous ice have been assigned by analogy with the assignments ofice I. E. WHALLEY. Can. J. Chem. 55, 3429 (1977). On propose une attribution detaillee des bandes d'elongation 0 -H en ir et en Raman des glaces desordonnees Ih et Ic. Cette attribution est basee sur l'hypothese que le spectre de la glace desordonnee Ic resemble beaucoup A celle de la glace ordonnee Ic et que le spectre qui n'a pas encore kt6 obtenu pour la glace ordonnee Ic peut 2tre predit A partir du spectre de la glace VIII.Les similarites supposees entre les spectres des glaces Ic ordonnee et dtsordonnee sont justifiees par la similarite observee dans les spectres des glaces VIII et VII qui sont respectivement les formes ordonnees et desordonnees de la mCme structure et sont tres reliees aux glaces Ic ordonnee et desordonnee. L'attribution rend compte du couplage intermoleculaire, qui est particulierement fort pour les vibrations v, mais faible pour v,, et le dedoublement TO-LO, en particulier des vibrations v,, qu'on demontre Ctre necessaire par consequence de la grande intensite du spectre infrarouge. On a attribue les bandes infrarouges et Raman de la glace amorphe par analogie avec les attributions de la glace I.[Traduit par le journal]

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Section: Disordered Ice Icmentioning

confidence: 99%

A detailed assignment of the O–H stretching bands of ice I

Whalley¹

1977

Can. J. Chem.

197

171

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“…Fe in equation (5) force constants (in N m-z) as given by Fifer & Schiffer (1970)" Fr=845"00; F,r=-10.47; F~,=16.72; F,= 75.40.…”

Section: V= 2v + 2ve=y~fxmentioning

confidence: 99%

“…However, the spectroscopic information is not detailed enough to make it possible to get information on the anharmonic part of the lattice perturbed intramolecular potential. We shall therefore assume, following Fifer & Schiffer (1970), that the anharmonicity is not significantly changed from what it is in the vapour.…”

Section: Introductionmentioning

confidence: 99%

The bonded water molecule. II. A simple model of the vibratory motion

Pedersen¹

1975

Acta Crystallogr Sect B

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The mean value of the HOH angle, (2e), is smaller than the observed value (Fig. 4) for both the NCA and the RBM model. This might at least partly explain why the H-O-H angle is generally observed to be about 3 ° larger when bound compared to the free molecule as pointed out in the Introduction. However, the correction factor is much larger for the NCA model than the RBM model.Comparing calculated and observed normal mode frequencies and U matrices for the atoms a representative value for k seems to be 20 N m-i (Pedersen, 1974). For this value of k the observed value of the OH distance will be 0.04 A shorter than the mean value and the observed HOH angle will be 2 ° larger than the mean. Compared to the average values reported by Ferraris & Franchini-Angela (1972) this implies that the corrected OH distance on the average is stretched 0.02 A and the corrected HOH angle is only enlarged 1.5 ° when the molecule is bonded. However, large variations have been observed in the geometry from one structure to another. It turns out to be difficult to systematize the observed variations. It is hoped that more reliable relations will be discovered from the geometry when the effect of motion has been corrected for. The correction must then be done as outlined above on the basis of a realistic potential fitted to the available information for each structure. A simple, quantitative model describing the vibratory motion of a water molecule bound in a condensed phase is presented. The model is based on a normal coordinate analysis of a bent XY2 molecule in a combined internal and external potential. The potential can be used to simulate the potential at a specific site in a crystal. Numerical values of the frequencies and eigenvectors, referred to Cartesian coordinates, are calculated from an isotropic external potential. The range of force constant in the external potential covered is from 0 to 50 N m-i. The force constants in the internal potential can be chosen to make the calculated frequencies of the internal modes equal to the observed values. The nine calculated normal modes can be divided into ~oups of three: intramolecular, torsional and translational. The calculated frequencies of the torsional and translational modes are in the range observed for librational modes. The translational and the intramolecular modes are coupled making the calculated intramolecular frequencies increase with the strength of the external potential using a constant internal potential. From the model, the mean square amplitudes of vibration of the individual atoms are calculated. The calculated values are found to be in the range observed in neutron-diffraction studies of hydrates.

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“…However, the differences between Ba(ClO,),~H,O and water vapor are in qualitative agreement with the trend pointed out in ref. 27.…”

Section: Vibrations Of Water Moleculesmentioning

confidence: 99%

“…The harmonic frequencies so obtained are shown in Table 3. The nine frequencies were fitted using the four force constants to yield the calculated frequencies and force constants shown on the right hand side of (Table 3), much smaller than the gasphase value of about -0.1 (27), and this clearly reflects the smaller v,' -v,' separation. The value of Frr cannot be compared with those given by Fifer and Schiffer for other hydrates, because of their different treatment of the anharmonicity and the very low weight assigned to v,' in their fitting procedure.…”

Section: Vibrations Of Water Moleculesmentioning

confidence: 99%

The Infrared and Raman Spectra of Powdered and Single-Crystal Barium Chlorate Monohydrate and -deuterate

Bertie¹,

Heyns²,

Oehler³

1973

Can. J. Chem.

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The infrared and Raman spectra of polycrystalline and single-crystal Ba(C103)2 .HzO and Ba(C103)'-.DzO have been obtained. The observed bands have been assigned to the various Davydov components of the intramolecular modes and colattice modes. For the water molecule, all of the fundamentals of H20, HDO, and DZO have been located, the anharmonicities of the bending modes have been determined, and those of the stretching modes are essentially the same as for water vapor. The intermolecular coupling is very weak. The effective harmonic force field for the water molecules has been calculated. The stretch-stretch interaction constant is much smaller than for water vapor, reflecting a smaller separation of the asymmetric and symmetric stretching modes. The intermolecular vibrations of the water molecules have been located. For the chlorate ions, in spite of the disorder due to the 37CI, the spectra can be interpreted in terms of unit cell modes, albeit as a first approximation. The isotope shift of the symmetric C1-0 stretching mode appears to be unusually large. The far-infrared spectra have been tentatively assigned to translational and rotational vibrations involving the BaZ+ and CI03-ions.Les spectres en infrarouge et en Raman ont Ct C obtenus pour les esptces polycristallines et monocristallines de Ba(C103)2.H20 et de Ba(CI03)Z.D20. Les bandes observees ont 6tC attribukes aux diverses composantes Davydov des modes intramolCculaires. Toutes les bandes fondamentales appartenant a l'HzO au HDO et au DzO ayant Ct C localisCes, on a pu dkterminer pour la molCci~le d'eau les anharmonicitks des modes de torsion; pour celles des modes d'Clongation, on a pu determiner qu'elles Ctaient identiques celles obtenues de la vapeur d'eau. Le couplage intermolCculaire est tres faible. O n a calculC, toujours pour les rnolCcules d'eau, le champ effectif de la force harmonique.La constante d'interaction elongation-Clongation est beaucoup plus petite que dans le cas de la vapeur d'eau, ce qui traduit une stparation plus faible des modes d'elongation asymitrique et symetrique. On a localise les vibrations intermoleculaires des molCcules d'eau. Pour les ions chlorates, malgrC la perturbation causee par la prCsence du 37C1, Ies spectres peuvent ttre interpret& en fonction des modes d'une maille eltmentaire, bien que ce ne soit possible qu'en premiere approximation. Le dkplacement isotopique du mode dlClongation symttrique du lien C1-0 semble ttre anormalement ClevC. Les spectres en lointain infrarouge ont CtC attribuCs hypothCtiquement aux mouvements de translation et de rotation des ions BaZ+ et C103-.

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Intramolecular Interactions in the Water Molecule: The Stretch–Stretch Interaction Force Constant of Water Molecules in Hydrogen-Bonded Systems

Cited by 35 publications

References 22 publications

A detailed assignment of the O–H stretching bands of ice I

A detailed assignment of the O–H stretching bands of ice I

The bonded water molecule. II. A simple model of the vibratory motion

The Infrared and Raman Spectra of Powdered and Single-Crystal Barium Chlorate Monohydrate and -deuterate

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