On the problem of the vibrational spectrum and structure of ice Ih: Lattice dynamical calculations

Bosi, P.; Tubino, R.; Zerbi, G.

doi:10.1063/1.1680666

Cited by 51 publications

(15 citation statements)

References 27 publications

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“…This interpretation of the absorption by translational lattice vibrations in crystals formed by orientationally disordered water molecules has recently been questioned by Zerbi and coworkers (20). These authors deny that the breadth of the features observed for ice 1 h (18) is evidence of the influence of the disorder.…”

Section: Resultsmentioning

confidence: 87%

The Far Infrared Spectra and X-Ray Powder Diffraction Patterns of the Structure I Hydrates of Cyclopropane and Ethylene Oxide at 100 °K

Bertie¹,

Bates²,

Hendricksen³

1975

Can. J. Chem.

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. Can. J. Chem. 53,71 (1975).This paper presents the far-infrared spectrum and X-ray powder diffraction pattern of the structure I hydrate of cyclopropane at 100 OK, and the powder diffraction pattern of the isostructural ethylene oxide hydrate at 100 O K . Between 360and 100cm-I the absorption by cyclopropane hydrate is essentially identical to that by ethylene oxide hydrate, but is shifted to low frequency by about 2%. This shift is undoubtedly related to the hydrogen bonds being slightly longer in cyclopropane hydrate, whose cubic lattice parameter is 11.98 + 0.02 Acompared to 11.89 + 0.02 Aforethyleneoxide hydrate, bothat 110 + 20°K. Theabsorption by cyclopropane hydrate below 100 cm-' decreases rapidly with decreasing frequency; this confirms that the absorption plateau observed for ethylene oxide hydrate between l00and about 50cm-I is due to primarily rotational vibrations of ethylene oxide. A recent statement, that the orientational disorder of the water molecules need not be invoked to explain the far infrared spectrum of ice 1 h, is disputed.

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Section: Resultsmentioning

confidence: 87%

The Far Infrared Spectra and X-Ray Powder Diffraction Patterns of the Structure I Hydrates of Cyclopropane and Ethylene Oxide at 100 °K

Bertie¹,

Bates²,

Hendricksen³

1975

Can. J. Chem.

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“…In H 2 O, the librations have considerably higher frequencies than in D 2 O, the highest observed frequency being 110 meV for H 2 O and 84 meV for D 2 O. 44 For this reason, we suspect that the energetic OX will lose its energy more easily to the H 2 O lattice than to the softer D 2 O lattice. The initially formed OD radical has greater initial energy (e.g., at 10 K, the averaged kinetic energy taken over the top four MLs is 0.263 eV, compared to 0.275 eV predicted from Eq.…”

Section: B Ox Radical Photodesorptionmentioning

confidence: 99%

“…(3) and considering vibrational excitation of the OD fragment, see above), and OH less initial energy (e.g., at 10 K, the averaged kinetic energy taken over the top four MLs is 0.200 eV, compared to a predicted value of 0.147 eV). However, the hyperthermal OD fragment formed will transfer its energy more easily to the H 2 O lattice, which has higher frequency librations (up to 110 meV 44 ), than OH will transfer its energy to the softer D 2 O lattice, which has lower frequency vibrations (up to 84 meV 44 ). We speculate that these opposing trends explain why the photodesorption probabilities of OD from an H 2 O ice system and OH from a D 2 O ice system are similar.…”

Section: B Ox Radical Photodesorptionmentioning

confidence: 99%

Isotope effects on the photodesorption processes of X2O (X = H,D) and HOD ice

Koning

Kroes

Arasa

2013

The Journal of Chemical Physics

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To investigate the isotope effects on the photodesorption processes of X 2 O (X = H,D) ice, molecular dynamics calculations have been performed on the ultraviolet photodissociation of an H 2 O or a D 2 O molecule in an H 2 O or a D 2 O amorphous ice surface, and on HOD photodissociation in an H 2 O amorphous ice surface, where the photodissociated molecules were located in the top four or five monolayers at ice temperatures of 10, 20, 30, 60, and 90 K. Three photodesorption processes can occur upon X 2 O photodissociation: X atom photodesorption, OX radical photodesorption, and X 2 O (or HOD) molecule photodesorption. X 2 O (or HOD) photodesorption can occur after recombination of X and OX, or after an energetic X atom photofragment kicks a surrounding X 2 O molecule from the ice surface. Isotope effects are observed for the X atom and the OX radical photodesorption as well as for the kick-out photodesorption. However, no isotope effects were noticeable for the photodesorption of recombined X 2 O molecules. The average D atom photodesorption probabilities are about a factor 0.9 smaller than those for the H atom, regardless of the isotope of the surrounding ice system. Also, the kick-out mechanism is more likely to occur if a D photofragment is created upon dissociation than if an H atom is created. These observations can be explained by more efficient energy transfer from the D atom to water molecules than from the H atom. Reasoning based on the X 2 O phonon frequencies associated with the librational modes and energy transfer efficiencies explain why the OX radical photodesorption probabilities are noticeably larger if the OX radical desorbs from a D 2 O ice system than from an H 2 O ice system. Also, the OX radical photodesorption is more probable upon dissociation of DOX (X = H,D) than upon dissociation of HOX (X = H,D), because the initial kinetic energy of the OX radical is larger if the dissociation products are D + OX than H + OX. The branching ratio of OD OH desorption following photodissociation of an HOD molecule in ice (about 1.0) is much lower than the OD OH branching ratio in gas-phase HOD photodissociation. This may lead to differences in isotope fractionation in OH(g) formation in dense and diffuse clouds in the interstellar medium.

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“…Model 3 has been used for ice Ih, 35 and was used only with force field B of ice II (Table VIII). It gave frequencies within 2 cm-I of those tabulated for model 1.…”

Section: B Calculation Of the Translational Vibrationsmentioning

confidence: 99%

“…We decided not to improve on our simple parametric force fields by including extra force constants, as has been done for ice Ih, 35 because there would be no independent indication of the correct values of these constants, Instead we decided to try Clementi's potentia1 39 for the interaction of two water molecules. We used the parameters given under the heading E:lnter in Table VIII of Ref.…”

Section: Calculation Of the Rotational And Translational Vibrationmentioning

confidence: 99%

Raman spectra of ices II and IX above 35 K at atmospheric pressure: Translational and rotational vibrations

Bertie¹,

Francis²

1982

The Journal of Chemical Physics

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The Raman scattering by the translational and rotational vibrations of normal and deuterated ice II and ice IX at atmospheric pressure and 35–100 K is reported. The infrared absorption by deuterated ice II and ice IX at atmospheric pressure and 4.3 K is also reported. Imperfect, but useful, polarized Raman spectra of single crystals of ice II have indicated the symmetries of the vibrations. The translational vibrations have been reproduced remarkably well by normal coordinate and intensity calculations based on very simple force fields and models of the dipole moment and polarizability changes. No features could be assigned to longitudinal optic modes. Attempts to calculate the rotational and translational vibrations from the one force field were made for five force fields. No force field reproduced the observed separation of translational and rotational displacements in the normal vibrations for the actual structure. This experimental fact, that the vibrations are translational or rotational but not mixed, will provide a severe test for potential functions for the interaction between water molecules. A correction is given to the sample temperature cited in a previous publication about the OH and OD stretching vibrations of these ices [J. E. Bertie and B. F. Francis, J. Chem. Phys. 72, 2213 (1980)].

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On the problem of the vibrational spectrum and structure of ice Ih: Lattice dynamical calculations

Cited by 51 publications

References 27 publications

The Far Infrared Spectra and X-Ray Powder Diffraction Patterns of the Structure I Hydrates of Cyclopropane and Ethylene Oxide at 100 °K

The Far Infrared Spectra and X-Ray Powder Diffraction Patterns of the Structure I Hydrates of Cyclopropane and Ethylene Oxide at 100 °K

Isotope effects on the photodesorption processes of X2O (X = H,D) and HOD ice

Raman spectra of ices II and IX above 35 K at atmospheric pressure: Translational and rotational vibrations

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