Structure Sensitivity in the Surface Chemistry of Ice: Acetone Adsorption on Amorphous and Crystalline Ice Films

Schaff, Jason E.; Roberts, Jeffrey T.

doi:10.1021/j100079a002

Cited by 75 publications

(93 citation statements)

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“…These assignments are confirmed by comparison with previous studies of the adsorption of water on metal surfaces as a function of adsorption temperature. [34][35][36][37][38] It is clear from the spectra shown in Figure 3B that it is possible to use the shape of the O-H stretching mode of water to identify the phase of the water. The spectrum recorded following adsorption at 150 K represents the fingerprint of pure CI and that recorded following adsorption at 100 K (or 130 K) represents the spectrum of pure ASW.…”

Section: Resultsmentioning

confidence: 99%

Reflection Absorption Infrared Spectroscopy and Temperature-Programmed Desorption Studies of the Adsorption and Desorption of Amorphous and Crystalline Water on a Graphite Surface

2005

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Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) have been used to perform a detailed investigation of the adsorption of water on highly oriented pyrolytic graphite (HOPG) at 90 K. RAIRS shows that water is physisorbed on HOPG at all coverages, as expected. Experiments at higher surface temperatures show marked changes in the O-H stretching region of the spectrum which can be assigned to the observation of the amorphous to crystalline ice phase transition. The infrared signature of both phases of solid water has been determined on HOPG and can be used to identify the phase of the ice. TPD spectra show the desorption of multilayers of crystalline ice. At high exposures a small bump appears in the TPD spectrum, on the low temperature side of the main peak, which is attributed to the amorphous to crystalline phase transition. At very low exposures of water, it is possible to distinguish the desorption of water from two-and three-dimensional islands and hence to determine the growth mode of water on the HOPG surface. Isothermal TPD studies have also been performed and show that the desorption of water does not obey perfect zero-order kinetics. Desorption orders, derived directly from the TPD spectra, confirm this observation. Desorption energies and preexponential factors have also been determined for this adsorption system.

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Section: Resultsmentioning

confidence: 99%

Reflection Absorption Infrared Spectroscopy and Temperature-Programmed Desorption Studies of the Adsorption and Desorption of Amorphous and Crystalline Water on a Graphite Surface

2005

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“…23 In Figure 1 are shown the OD stretching regions of the infrared spectra of two 20 ML ice films made of fully deuterated water (ice-d 2 ) deposited on Pt(111). The upper spectrum was obtained after allowing room-temperature water vapor to condense on the 130 K substrate, and the bottom spectrum after briefly heating the same ice film to 173 K. 24 The broad absorption bands between 2300 and 2700 cm -1 are attributed mostly to the OD stretching vibrations in hydrogen-bonded D 2 O in the thin film bulk. Differences between the two spectra in this frequency region are associated with bulk structure: D 2 O condenses at 130 K as an amorphous, metastable phase, while heating to 173 K induces crystallization to hexagonal or cubic ice.…”

Section: Experimental Approachmentioning

confidence: 99%

Chemistry at the Surfaces of Ice and Sulfuric Acid: Toward an Understanding of Adsorption at Molecular Solids

Roberts

1998

Acc. Chem. Res.

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“…13 In the case when strong H-bonding is involved in the adsorption of a guest species, the red shift in the OH dangling bond is expected to increase. 12 The weak OH dangling-bond feature for a guest species (e.g., acetone) upon adsorption on ice could then be obscured by the much stronger OH stretch feature of the bulk if the magnitude of the red-shift happens to be large. 12 Moreover, the CO stretch of carbon monoxide adsorbed on NCI was found to be a doublet at 2153 and 2137 cm -1 , corresponding to adsorption at two different types of sites.…”

Section: Introductionmentioning

confidence: 99%

“…12 The weak OH dangling-bond feature for a guest species (e.g., acetone) upon adsorption on ice could then be obscured by the much stronger OH stretch feature of the bulk if the magnitude of the red-shift happens to be large. 12 Moreover, the CO stretch of carbon monoxide adsorbed on NCI was found to be a doublet at 2153 and 2137 cm -1 , corresponding to adsorption at two different types of sites. 10 The band at 2153 cm -1 is found to locate at a similar position to those of the corresponding CO stretch for CO complexes with HF, HCl, and HBr at low temperature (12 K), 17 in which CO acts as a proton acceptor to the OH dangling bond of the ice substrate.…”

Section: Introductionmentioning

confidence: 99%

Thermal Evolution of Acetic Acid Nanodeposits over 123−180 K on Noncrystalline Ice and Polycrystalline Ice Studied by FTIR Reflection−Absorption Spectroscopy: Hydrogen-bonding Interactions in Acetic Acid and between Acetic Acid and Ice

Gao

2005

J. Phys. Chem. B

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Acetic acid vapor-deposited on ultrathin noncrystalline ice (NCI) and polycrystalline ice (PCI) films (less than 6 nm thick) under ultrahigh vacuum conditions has been investigated by using Fourier Transform Infrared Reflection-Absorption Spectroscopy. Pristine acetic acid deposited at 123 K (on a copper support) appears as an amorphous solid, which undergoes an irreversible phase transformation to a more structurally ordered (polycrystalline) form upon annealing to 153 K. Acetic acid is found to adsorb on NCI and PCI films initially through hydrogen bonding between CdO and dangling OH (of ice), followed by the formation of multilayers at 123 K. Thermal evolution studies of a low exposure of acetic acid on the ultrathin NCI and PCI films show that acetic acid undergoes coevaporation with water likely as an acetic acid hydrate at 155 K, which continues until the entire ice film has been exhausted at 165 K. Above 165 K, the remaining acetic acid solid appears to evaporate without undergoing the phase transformation, in contrast to the case of a high acetic acid exposure. Coevaporation of acetic acid with water is also found to proceed at a faster rate than the subsequent evaporation of acetic acid, which is consistent with the weaker interactions observed in the H-bonded acetic acid hydrate than that in acetic acid solid.

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Structure Sensitivity in the Surface Chemistry of Ice: Acetone Adsorption on Amorphous and Crystalline Ice Films

Cited by 75 publications

References 0 publications

Reflection Absorption Infrared Spectroscopy and Temperature-Programmed Desorption Studies of the Adsorption and Desorption of Amorphous and Crystalline Water on a Graphite Surface

Reflection Absorption Infrared Spectroscopy and Temperature-Programmed Desorption Studies of the Adsorption and Desorption of Amorphous and Crystalline Water on a Graphite Surface

Chemistry at the Surfaces of Ice and Sulfuric Acid: Toward an Understanding of Adsorption at Molecular Solids

Thermal Evolution of Acetic Acid Nanodeposits over 123−180 K on Noncrystalline Ice and Polycrystalline Ice Studied by FTIR Reflection−Absorption Spectroscopy: Hydrogen-bonding Interactions in Acetic Acid and between Acetic Acid and Ice

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