Biomedical subjects

Patrick Ayotte

Publications and source records attributed to Patrick Ayotte.

6 recordsLinked to original sources

PubMed2006

Diffusion kinetics for methanol in polycrystalline ice.

Quantitative analyses of the isothermal desorption kinetics from methanol-doped H2O films on Pt(111) reveal that transport kinetics for CH3OH in polycrystalline ice are much slower than previously reported. They also indicate that MeOH displays first-order desorption kinetics with respect to its instantaneous surface concentration below 0.1 mole fraction in ice. These observations allow isothermal desorption rate measurements to be interpreted in terms of a depth profiling analysis providing one-dimensional concentration depth profiles from methanol-doped polycrystalline ice films. Using a straightforward approach to inhibit ice sublimation, transport properties are extracted from the evolution of concentration depth profiles obtained after thermal annealing of binary ice films at high temperature. Heterodiffusion coefficients for methanol in polycrystalline (cubic) ice Ic films are reported for temperatures between 145 and 195 K and for concentrations below 10(-3) mole fraction. Finally, diffusion kinetics for methanol in ice are shown to display a very strong concentration dependence that may contribute, in addition to variations in laboratory samples microstructure, to the disagreements reported in the literature regarding the transport properties of ice.

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PubMed2005

What determines the sticking probability of water molecules on ice?

We present both experimental and theoretical studies of the sticking of water molecules on ice. The sticking probability is unity over a wide range in energy (0.5 eV-1.5 eV) when the molecules are incident along the surface normal, but drops as the angle increases at high incident energy. This is explained in terms of the strong orientational dependence of the interaction of the molecule with the surface and the time required for the reorientation of the molecule. The sticking probability is found to scale with the component of the incident velocity in the plane of the surface, unlike the commonly assumed normal or total energy scaling.

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PubMed2005

Why is hydrofluoric acid a weak acid?

The infrared vibrational spectra of amorphous solid water thin films doped with HF at 40 K reveal a strong continuous absorbance in the 1000-3275 cm(-1) range. This so-called Zundel continuum is the spectroscopic hallmark for aqueous protons. The extensive ionic dissociation of HF at such low temperature suggests that the reaction enthalpy remains negative down to 40 K. These observations support the interpretation that dilute HF aqueous solutions behave as weak acids largely due to the large positive reaction entropy resulting from the structure making character of the hydrated fluoride ion.

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PubMed2005

Adsorption and desorption of HCl on Pt(111).

The adsorption and desorption of HCl on Pt(111) is investigated by temperature programmed desorption, infrared reflection absorption spectroscopy, and low energy electron diffraction. Five peaks are identified in the desorption spectra prior to the onset of multilayer desorption. At low coverage ( < 0.25 monolayers (ML)), desorption peaks at approximately 135 and 200 K are observed and assigned to recombinative desorption of dissociated HCl. At higher coverages, desorption peaks at 70, 77, and 84 K are observed. These peaks are assigned to the desorption of molecularly adsorbed HCl. The infrared spectra are in agreement with these assignments and show that HCl deposited at 20 K is amorphous but crystallizes when heated above 60 K. Kinetic analysis of the desorption spectra reveals a strong repulsive coverage dependence for the desorption energy of the low coverage features ( < 0.25 ML). The diffraction data indicate that at low temperature the adsorbed HCl clusters into ordered islands with a (3 x 3) structure and a local coverage of 4/9 with respect to the Pt(111) substrate.

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PubMed2004

Helium diffusion through H2O and D2O amorphous ice: observation of a lattice inverse isotope effect.

The diffusion of He through both H2O and D2O amorphous solid water (ASW) has been measured between 55 and 110 K. We find the diffusion rate is dependent on the isotopic composition of the ASW lattice. This lattice isotope effect is the "inverse" of a normal isotope effect in that diffusion is faster in the heavier (D2O) isotope. Transition state theory calculations show that the inverse isotope effect is due to a tight transition state and predominantly arises from the zero-point vibrational energy associated with the frustrated rotational modes of water in the lattice.

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PubMed2002

A beaker without walls: formation of deeply supercooled binary liquid solutions of alcohols from nanoscale amorphous solid films.

Layered nanoscale amorphous solid films of methanol and ethanol undergo complete intermixing prior to the onset of measurable desorption at 120 K. This intermixing precedes and inhibits crystallization. Subsequent desorption of the film is described quantitatively by a kinetic model describing evaporation from a continuously mixed ideal binary liquid solution. This occurs at temperatures below the melting point of the binary mixture, indicating ideal behavior for the supercooled liquid solution. This approach provides a new method for preparing and examining deeply supercooled solutions.

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