Zdenek Dohnalek

Control of amorphous solid water morphology using molecular beams. I. Experimental results

The adsorption of N2 was used to investigate the porosity/morphology of thin films of amorphous solid water. Molecular beams were used to vapor deposit amorphous solid water films on a Pt(111) crystal at a variety of incident growth angles. The amount of N2 adsorbed by the amorphous solid water depends very sensitively on the growth angle and thermal history of the film. For normal and nearly normal incidence growth, the water films are relatively dense and smooth and adsorb only a small amount of N2. For larger growth angles, the films are porous and adsorb large quantities of N2 with apparent surface areas as high as ∼2700 m2/g. The physical and chemical properties of amorphous solid water are of interest because of its presence in astrophysical environments. The observations have important implications for laboratory studies which use vapor deposited amorphous solid water films as analogs for astrophysical icy bodies such as comets.

The deposition angle-dependent density of amorphous solid water films

The index of refraction and thickness of amorphous solid water (ASW) films are determined using laser optical interferometry. From the film thickness, the density of ASW can be calculated directly since the molecular beam flux and the H2O condensation coefficient are both known. From the index of refraction the ASW density can also be determined using the Lorentz–Lorenz relationship. The densities determined via both methods agree within experimental uncertainty. For films deposited at 22 K using a collimated molecular beam, the index of refraction and density decrease monotonically as the deposition angle is varied from normal to oblique incidence. At normal incidence the films have an index of refraction of 1.285 and are presumed to be fully dense (0.94 g/cm3). At glancing incidence (86°) the film has a refractive index of 1.05 and a density of 0.16 g/cm3, indicating a porosity exceeding 80%. The angle-dependent film density is in semiquantitative agreement with the results of ballistic deposition simul...

n-alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters

We have measured the desorption of seven small n-alkanes (C(N)H(2N+2), N=1-4,6,8,10) from the Pt(111) and C(0001) surfaces by temperature programed desorption. We compare these results to our recent study of the desorption kinetics of these molecules on MgO(100) [J. Chem. Phys. 122, 164708 (2005)]. There we showed an increase in the desorption preexponential factor by several orders of magnitude with increasing n-alkane chain length and a linear desorption energy scaling with a small y-intercept value. We suggest that the significant increase in desorption prefactor with chain length is not particular to the MgO(100) surface, but is a general effect for desorption of the small n-alkanes. This argument is supported by statistical mechanical arguments for the increase in the entropy gain of the molecules upon desorption. In this work, we demonstrate that this hypothesis holds true on both a metal surface and a graphite surface. We observe an increase in prefactor by five orders of magnitude over the range of n-alkane chain lengths studied here. On each surface, the desorption energies of the n-alkanes are found to increase linearly with the molecule chain length and have a small y-intercept value. Prior results of other groups have yielded a linear desorption energy scaling with chain length that has unphysically large y-intercept values. We demonstrate that by allowing the prefactor to increase according to our model, a reanalysis of their data resolves this y-intercept problem to some degree.

n-alkanes on MgO(100). II. Chain length dependence of kinetic desorption parameters for small n-alkanes

Coverage-dependent desorption-kinetics parameters are obtained from high-quality temperature-programmed desorption data for seven small n-alkane molecules on MgO(100). The molecules, CNH2N+2 (N=1-4,6,8,10), were each studied for a set of 29 initial coverages at a heating ramp rate of 0.6 K/s as well as at a set of nine ramp rates in the range of 0.3-10.0 K/s. The inversion analysis method with its least-squares preexponential factor (prefactor) optimization discussed in the accompanying article is applied to these data. This method allows for accurate determination of prefactors and coverage-dependent desorption energies. The prefactor for desorption increases dramatically with chain length from 10(13.1) to 10(19.1) s(-1) over the range of N=1-10. We show that this increase can be physically justified by considering the increase in rotational entropy available to the molecules in the gaslike transition state for desorption. The desorption energy increases with chain length as Ed(N)=6.5+7.1N, which implies an incremental increase of 7.1+/-0.2 kJ/mol per CH2.

Control of amorphous solid water morphology using molecular beams. II. Ballistic deposition simulations

Ballistic deposition simulations of thin film growth were performed. The results of the simulations are compared to experiments of N2 adsorption by porous amorphous solid water thin films. The simulations are in qualitative agreement with the experimental observations: The porosity of the thin films is controlled by using a collimated beam to vapor deposit the films. Films with normal or near normal growth angles (θ∼0°) are relatively dense and smooth. Films with larger growth angles are highly porous and the average pore size increases as the growth angle increases. The simulations indicate that for growth angles greater than ∼70°, adsorption into the largest pores is not possible leading to the experimentally observed maximum in N2 adsorption by porous amorphous solid water at θ=70°.

Intrinsic Diffusion of Hydrogen on Rutile TiO2(110)

The combined experimental and theoretical study of intrinsic hydrogen diffusion on bridge-bonded oxygen (BBO) rows of TiO 2(110) is presented. Sequences of isothermal scanning tunneling microscopy images demonstrate a complex behavior of hydrogen formed by water dissociation on BBO vacancies. Different diffusion rates are observed for the two hydrogens in the original geminate OH pair suggesting the presence of a long-lived polaronic state. For the case of separated hydroxyls, both theory and experiment yield comparable temperature-dependent diffusion rates. Density functional theory calculations show that there are two comparable low energy diffusion pathways for hydrogen motion along the BBO from one BBO to its neighbor, one by a direct hop and the other by an intermediate minimum at a terrace O. The values of kinetic parameters (prefactors and diffusion barriers) determined experimentally and theoretically are significantly different and indicate the presence of a more complex diffusion mechanism. We speculate that the hydrogen diffusion proceeds via a two-step mechanism: the initial diffusion of localized charge, followed by the diffusion of hydrogen. Both experiment and theory show the presence of repulsive OH-OH interactions.

n-alkanes on MgO(100). I. Coverage-dependent desorption kinetics of n-butane

High-quality temperature-programmed desorption (TPD) measurements of n-butane from MgO(100) have been made for a large number of initial butane coverages (0-3.70 ML, ML-monolayers) and a wide range of heating ramp rates (0.3-10 K/s). We present a TPD analysis technique which allows the coverage-dependent desorption energy to be accurately determined by mathematical inversion of a TPD spectrum, assuming only that the preexponential factor (prefactor) is coverage independent. A variational method is used to determine the prefactor that minimizes the difference between a set of simulated TPD spectra and corresponding experimental data. The best fit for butane desorption from MgO is obtained with a prefactor of 10(15.7+/-1.6) s(-1). The desorption energy is 34.9+/-3.4 kJ/mol at 0.5-ML coverage, and varies with coverage approximately as Ed(theta)=34.5+0.566theta+8.37 exp(-theta/0.101). Simulations based on these results can accurately reproduce TPD experiments for submonolayer initial coverages over a wide range of heating ramp rates (0.3-10 K/s). Advantages and limitations of this method are discussed.

Effect of porosity on the adsorption, desorption, trapping, and release of volatile gases by amorphous solid water

We compare the adsorption, desorption, trapping, and release of Ar, N 2 , O 2 , CO, and CH 4 by dense (nonporous) and highly porous amorphous solid water (ASW) films. Molecular beam deposition techniques are used to control the porosity of the vapor-deposited ASW thin films. Experiments where the gas species is deposited on top of and underneath dense and porous ASW are conducted. For the film thickness used in this study, the porous films are found to adsorb between 20 and 50 times more gas than the dense films. The desorption temperature of the adsorbed gas is also dependent on the porosity of the ASW film. Differences between desorption from porous and dense ASW films are attributed to differences in their ability to trap weakly physisorbed gases. The results are largely independent of the gas studied, confirming that the adsorption and trapping of gases are dominated by the ASW porosity. These findings show that laboratory studies must account for the growth conditions and their effects on ASW morphology in order to accurately predict the properties of astrophysical ices.

The Self-diffusivity of Amorphous Solid Water Near 150 K

Abstract Molecular beam techniques are used to create nanoscale thin films composed of different isotopes of amorphous solid water (ASW). The metastable ASW composites are then heated above the glass transition temperature, T g , and the extent of isotopic intermixing is determined using temperature programmed desorption. The observed self-diffusion in the 150–160 K range is roughly a millionfold greater than that expected for crystalline ice. The magnitude and temperature dependence of the self-diffusivity are consistent with an amorphous solid that melts into a deeply supercooled liquid prior to crystallization. The overall temperature dependence for the diffusivity of liquid water, supercooled liquid water (238–273 K), and of ASW (150–160 K) is well described by the Vogel–Fulcher–Tamman equation. These results suggest that ASW above its T g is a deeply supercooled metastable extension of normal liquid water prior to crystallizing near 160 K. Additionally, rapid H/D isotopic exchange occurs in concert with the translational diffusive motion.

Substrate induced crystallization of amorphous solid water at low temperatures

We show that N2 monolayer desorption from ice surfaces is a quantitative, highly sensitive method for following the surface crystallization kinetics at low temperatures. Vapor deposited water films on a crystalline ice substrate exhibit amorphous growth at temperatures below ∼110 K. The rate of crystallization for these amorphous films is dramatically accelerated compared to the rate of crystallization observed for the amorphous films deposited directly on Pt(111). We find that the crystalline ice substrate acts as a two-dimensional nucleus for the growth of the crystalline phase, thereby accelerating the crystallization kinetics.