Acetone and water on TiO2(110): H/D exchange

Isotopic H/D exchange between coadsorbed acetone and water on the TiO2(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (O2 oxidation and mild vacuum reduction). Coadsorbed acetone and water interact repulsively on reduced TiO2(110) on the basis of results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 monolayers (ML) of a 1 ML d6-acetone on the reduced surface (vacuum annealed at 850 K to a surface oxygen vacancy population of 7%) exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in the high-temperature region of the d6-acetone TPD spectrum at approximately 340 K. The effect was confirmed with combinations of d0-acetone and D2O. The extent of exchange decreased on the reduced surface for water coverages above approximately 0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when surface oxygen vacancies were pre-oxidized with O2 prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d1- or d5-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at approximately 390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites, and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange mechanism likely involves an enolate or propenol surface intermediate formed transiently during the desorption of oxygen-stabilized acetone molecules.     

Application of the hypernetted chain approximation to the electrical double layer for 2:1 and 1:2 electrolytes

The equations needed to estimate the potential drop across the diffuse layer according to the hypernetted chain approximation (HNCA) are derived in this paper for 2:1 and 1:2 electrolytes at the restricted primitive level. It is shown that HNCA results can be expressed in the same format as the corresponding Gouy-Chapman equations with inclusion of two modifying functions. One function depends on the fraction of the solution volume occupied by the ions, and the other depends on the reciprocal thickness of the ionic atmosphere surrounding each ion. In addition, an expression for the potential profile in the diffuse layer for 2:1 and 1:2 electrolyte solutions is derived according to Gouy-Chapman theory. The modifying functions in the HNCA are then estimated using the Henderson-Blum approach for solutions containing ions with diameters of 300 and 400 pm for concentrations in the range from 0.1 to 2 M. It is shown that the Henderson-Blum approach is inadequate for systems with multivalent ions except for charge densities very close to the point of zero charge.     

Charge compensation and the luminescence of Cr3+ in KMgF3

Studies of the photoluminescence spectra of Cr³⁺ ions in KMgF₃ crystals co-doped with Cr³⁺ and Ni²⁺ ions are reported. Several crystal field sites are identified by the different R-line spectra due to the ² E⁴ A ₂ transition and broadband luminescences associated with the ⁴ T ₂⁴ A ₂ transitions. Cr³⁺ ions substituting without local charge compensation on the octahedral Mg²⁺ site give rise to a low temperature R line in photoluminescence at =702.3 nm with a radiative decaytime of 3 ms at T=14 K. At T=300 K this isotropic centre gives rise to an unpolarized broadband ⁴ T ₂⁴ A ₂ emission, which results from the thermal occupancy of an excited ⁴ T ₂ state just above the ² E level which, at lower temperature, gives rise to emission in the R-line. Other crystal field sites are due to some Cr³⁺ ions having Mg²⁺ or K⁺ vacancies in nearest-neighbour positions, these vacancies being required to maintain charge neutrality in doped fluoride perovskites. The Cr³⁺–K⁺ vacancy complex results in the centre having trigonal symmetry, and low temperature, photoluminescence via R ₁ and R ₂ lines at 716.8 nm and 716.0 nm, respectively. Finally, Cr³⁺ ions having a nearest neighbour Mg²⁺ vacancy have tetragonal symmetry, experiencing weak crystal fields. In consequence, the ⁴ T ₂ level lies below ² E and the photoluminescence spectrum at low temperature takes the form of a polarized broad ⁴ T ₂⁴ A ₂ band with peak at 760 nm and radiative decaytime of 54 s.