The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔGr acquired from increasing versus decreasing disequilibrium positions.
In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure. 相似文献
A six level rate equation system was used to investigate the impact of photodepletion to amplified spontaneous emission (ASE)
of intramolecular proton-transfer (IPT) dyes incorporated into polymeric hosts. The model includes the most important transitions
for the normal and tautomer form of the molecule as well as intersystem crossing and triplet–triplet transitions. The experimentally
observed pulse shape as well as photodepletion phenomena, i.e. a first order exponential decay of the ASE intensity and a
shortening in ASE pulse width, have been simulated successfully. Additionally, the model was used to propose an explanation
of the unexpected high photodepletion of proton-transfer dyes in solids. The results show that the emission cross section
and reabsorption cross section of the tautomer form of the molecule are the most important parameter not only for efficiency
but also for photodepletion. The model was tested by comparison with experimental results of 2-(2’-hydroxyphenyl)benzimidazole
in polymethylmethacrylate (PMMA), polystyrene (PS) and a 1:1 alternating copolymer matrix PS-co-PMMA.
PACS 78.45.th; 42.55.Mv; 42.70.Jk 相似文献
Hyperfine Interactions - In this paper, the conditions for which three-dimensional crystalline ion beams were attained in the rf quadrupole storage ring PALLAS at a velocity of around 2800 m/s are... 相似文献
It is shown that, if a parametrized fämily of extremals F can be stratified in a way compatible with the flow map generated by F, then those trajectories of the family which realize the minimal values of the cost in F are indeed optimal in comparison with all trajectories which lie in the region R covered by the trajectories of F. It is not assumed that F is a field covering the state space injectively. As illustration, an optimal synthesis is constructed for a system where the flow of extremals exhibits a simple cusp singularity. 相似文献
A model for parallel and distributed programs, the dynamic process graph (DPG), is investigated under graph-theoretic and complexity aspects. Such graphs embed constructors for parallel programs, synchronization mechanisms as well as conditional branches. They are capable of representing all possible executions of a parallel or distributed program in a very compact way. The size of this representation can be as small as logarithmic with respect to the size of any execution of the program.
In a preceding paper [A. Jakoby, et al., Scheduling dynamic graphs, in: Proc. 16th Symposium on Theoretical Aspects in Computer Science STACS'99, LNCS, vol. 1563, Springer, 1999, pp. 383–392] we have analysed the expressive power of the general model and various variants of it. We have considered the scheduling problem for DPGs given enough parallelism taking into account communication delays between processors when exchanging data. Given a DPG the question arises whether it can be executed (that means whether the corresponding parallel program has been specified correctly), and what is its minimum schedule length.
In this paper we study a subclass of dynamic process graphs called
-output DPGs, which are appropriate in many situations, and investigate their expressive power. In a previous paper we have shown that the problem to determine the minimum schedule length is still intractable for this subclass, namely this problem is
-complete as is the general case. Here we will investigate structural properties of the executions of such graphs. A natural graph-theoretic conjecture that executions must always split into components that are isomorphic to subgraphs turns out to be wrong. We are able to prove a weaker property. This implies a quadratic upper bound on the schedule length that may be necessary in the worst case, in contrast to the general case, where the optimal schedule length may be exponential with respect to the size of the representing DPG. Making this bound constructive, we obtain an approximation to a
-complete problem. Computing such a schedule and then executing the program can be done on a parallel machine in polynomial time in a highly distributive fashion. 相似文献
We determine the stationary two-point correlation function of the one-dimensional KPZ equation through the scaling limit of a solvable microscopic model, the polynuclear growth model. The equivalence to a directed polymer problem with specific boundary conditions allows one to express the corresponding scaling function in terms of the solution to a Riemann–Hilbert problem related to the Painlevé II equation. We solve these equations numerically with very high precision and compare our, up to numerical rounding exact, result with the prediction of Colaiori and Moore(1) obtained from the mode coupling approximation. 相似文献
Ceramic finds from the Galería de las Ofrendas at Chavín de Huántar and surface finds from the settlement of Chavín were characterised by combining the results of archaeological typology with archaeometric studies using neutron activation analysis, Mössbauer spectroscopy, X-ray diffraction and thin-section microscopy. Sherds from the pyramid Tello are included in the study as representative of local material. The analyses show that the vessels were made from different raw materials and that different firing procedures were used in their production. Sherds of certain styles largely exhibit similar types of Mössbauer patterns and in many instances also have similar element compositions. This supports the archaeological notion that the vessels were brought to Chavín from the provinces, perhaps on the occasion of a festivity. 相似文献