Third-order pump-probe spectroscopy applied to molecular dimers: characterization of relaxation dynamics and exciton-exciton annihilation.

We investigate theoretically the excitonic dynamics in molecular dimers which is monitored by two time-delayed femtosecond laser pulses. A two-photon absorption leads to a wave packet dynamics in the manifold of second excited states. This opens up the channel for exciton-exciton annihilation (EEA) which involves non-radiative electronic transitions. It is shown that the time interval during which EEA takes place can be monitored by the detection of third-order signals which can be interpreted as originating from a pump-probe scheme. In the case of transient absorption, the spectra directly map intraband relaxation processes.

Optically Induced Electron Transfer in Mixed-Valence States: A Model Study on Electronic Transitions, Relaxation Dynamics, and Transient Absorption Spectroscopy.

Quantum dynamical model calculations are performed on the optically induced electron transfer in a mixed-valence system interacting with different solvents. The simultaneously occurring processes of population transfer between electronic states and relaxation are studied in detail. Transient absorption traces, as recently recorded in our laboratory, are simulated, and the features of the spectra are related to the dynamics. The agreement with the experiment hints at the fact that the employed one-dimensional models catch the essentials of the photochemistry of the investigated systems and that they can be used for the interpretation of the transient absorption spectra. It is inferred that the ultrafast electron transfer processes take place on a sub-picosecond time scale and afterward relaxation occurs within several picoseconds.

Release of Isonitrile- and NHC-Stabilized Borylenes from Group†VI Terminal Borylene Complexes.

A family of doubly isonitrile-stabilized terphenyl borylenes could be obtained by addition of three equivalents of isonitrile to the corresponding Cr and W terminal terphenyl-borylene complexes. The mechanism of isonitrile- and carbon-monoxide-induced borylene liberation was investigated computationally and found to be significantly exergonic in both cases. Furthermore, addition of a small N-heterocyclic carbene (NHC) to a terminal Cr borylene complex results in release of an NHC-stabilized borylene carbonyl species, whereas the analogous reaction with bulkier phosphines results in metal-centered substitution.

Precipitation and Crystallization Kinetics in Silica Gardens.

Silica gardens are extraordinary plant-like structures resulting from the complex interplay of relatively simple inorganic components. Recent work has highlighted that macroscopic self-assembly is accompanied by the spontaneous formation of considerable chemical gradients, which induce a cascade of coupled dissolution, diffusion, and precipitation processes occurring over timescales as long as several days. In the present study, this dynamic behavior was investigated for silica gardens based on iron and cobalt chloride by means of two synchrotron-based techniques, which allow the determination of concentration profiles and time-resolved monitoring of diffraction patterns, thus giving direct insight into the progress of dissolution and crystallization phenomena in the system. On the basis of the collected data, a kinetic model is proposed to describe the relevant reactions on a fundamental physicochemical level. The results show that the choice of the metal cations (as well as their counterions) is crucial for the development of silica gardens in both the short and long term (i.e. during tube formation and upon subsequent slow equilibration), and provide important clues for understanding the properties of related structures in geochemical and industrial environments.

Growth behavior and kinetics of self-assembled silica-carbonate biomorphs.

Upon slow crystallization from silica-containing solutions or gels at elevated pH, alkaline-earth carbonates spontaneously self-assemble into remarkable nanocrystalline ultrastructures. These so-called silica biomorphs exhibit curved morphologies beyond crystallographic symmetry and ordered textures reminiscent of the hierarchical design found in many biominerals. The formation of these fascinating materials is thought to be driven by a dynamic coupling of the components' speciations in solution, which causes concerted autocatalytic mineralization of silica-stabilized nanocrystals over hours. In the present work, we have studied the precipitation kinetics of this unique system by determining growth rates of individual aggregates using video microscopy, and correlated the results with time-dependent data on the concentration of metal ions and pH acquired online during crystallization. In this manner, insight to the evolution of chemical conditions during growth was gained. It is shown that crystallization proceeds linearly with time and is essentially reaction controlled, which fits well in the proposed morphogenetic scenario, and thus, indirectly supports it. Measurements of the silica concentration in solution, combined with analyses of crystal aggregates isolated at distinct stages of morphogenesis, further demonstrate that the fraction of silica coprecipitated with carbonate during active growth is rather small. We discuss our findings with respect to the role of silica in the formation of biomorphs, and moreover, prove that the external silica skins that occasionally sheath the aggregates--previously supposed to be involved in the growth mechanism--originate from secondary precipitation after growth is already terminated.

Dynamic diffusion and precipitation processes across calcium silicate membranes.

HYPOTHESIS: Chemical gardens are tubular inorganic structures exhibiting complex morphologies and interesting dynamic properties upon ageing, with coupled diffusion and precipitation processes keeping the systems out of equilibrium for extended periods of time. Calcium-based silica gardens should comprise membranes that mimic the microstructures occurring in ordinary Portland cement and/or silicate gel layers observed around highly reactive siliceous aggregates in concrete. EXPERIMENTS: Single macroscopic silica garden tubes were prepared using pellets of calcium chloride and sodium silicate solution. The composition of the mineralized tubes was characterized by means of various ex-situ techniques, while time-dependent monitoring of the solutions enclosed by and surrounding the membrane gives insight into the spatiotemporal distribution of the different ionic species. The latter data reflect transport properties and precipitation reactions in the system, thus allowing its complex dynamic behavior to be resolved. FINDINGS: The results show that in contrast to the previously studied cases of iron- and cobalt-based silica gardens, the formed calcium silicate membrane is homogeneous and ultimately becomes impermeable to all species except water, hydroxide and sodium ions, resulting in the permanent conservation of considerable concentration gradients across the membrane. The insights gained in this work may help elucidate the nature and mechanisms of ion diffusion in Portland cements and concrete, especially those occurring during initial hydration of calcium silicates and the so-called alkali-silica reaction (ASR), one of the major concrete deterioration mechanisms causing serious problems with respect to the durability of concrete and the restricted use of many potential sources of raw materials.

Stabilization of amorphous calcium carbonate in inorganic silica-rich environments.

In biomineralization, living organisms carefully control the crystallization of calcium carbonate to create functional materials and thereby often take advantage of polymorphism by stabilizing a specific phase that is most suitable for a given demand. In particular, the lifetime of usually transient amorphous calcium carbonate (ACC) seems to be thoroughly regulated by the organic matrix, so as to use it either as an intermediate storage depot or directly as a structural element in a permanently stable state. In the present study, we show that the temporal stability of ACC can be influenced in a deliberate manner also in much simpler purely abiotic systems. To illustrate this, we have monitored the progress of calcium carbonate precipitation at high pH from solutions containing different amounts of sodium silicate. It was found that growing ACC particles provoke spontaneous polymerization of silica in their vicinity, which is proposed to result from a local decrease of pH nearby the surface. This leads to the deposition of hydrated amorphous silica layers on the ACC grains, which arrest growth and alter the size of the particles. Depending on the silica concentration, these skins have different thicknesses and exhibit distinct degrees of porosity, therefore impeding to varying extents the dissolution of ACC and energetically favored transformation to calcite. Under the given conditions, crystallization of calcium carbonate was slowed down over tunable periods or completely prevented on time scales of years, even when ACC coexisted side by side with calcite in solution.

The effect of silica on polymorphic precipitation of calcium carbonate: an on-line energy-dispersive X-ray diffraction (EDXRD) study.

Calcium carbonate is the most abundant biomineral and a compound of great industrial importance. Its precipitation from solution has been studied extensively and was often shown to proceed via distinct intermediate phases, which undergo sequential transformations before eventually yielding the stable crystalline polymorph, calcite. In the present work, we have investigated the crystallisation of calcium carbonate in a time-resolved and non-invasive manner by means of energy-dispersive X-ray diffraction (EDXRD) using synchrotron radiation. In particular, the role of silica as a soluble additive during the crystallisation process was examined. Measurements were carried out at different temperatures (20, 50 and 80 °C) and various silica concentrations. Experiments conducted in the absence of silica reflect the continuous conversion of kinetically formed metastable polymorphs (vaterite and aragonite) to calcite and allow for quantifying the progress of transformation. Addition of silica induced remarkable changes in the temporal evolution of polymorphic fractions existing in the system. Essentially, the formation of calcite was found to be accelerated at 20 °C, whereas marked retardation or complete inhibition of phase transitions was observed at higher temperatures. These findings are explained in terms of a competition between the promotional effect of silica on calcite growth rates and kinetic stabilisation of vaterite and aragonite due to adsorption (or precipitation) of silica on their surfaces, along with temperature-dependent variations of silica condensation rates. Data collected at high silica concentrations indicate the presence of an amorphous phase over extended frames of time, suggesting that initially generated ACC particles are progressively stabilised by silica. Our results may have important implications for CaCO3 precipitation scenarios in both geochemical and industrial settings, where solution silicate is omnipresent, as well as for CO2 sequestration technologies.

Experimental techniques for the growth and characterization of silica biomorphs and silica gardens.

Silica biomorphs and silica gardens are canonical examples of precipitation phenomena yielding self-assembled nanocrystalline composite materials with outstanding properties in terms of morphology and texture. Both types of structures form spontaneously in alkaline environments and rely on simple, and essentially similar, chemistry. However, the underlying growth processes are very sensitive to a range of experimental parameters, distinct preparation procedures, and external conditions. In this chapter, we report detailed protocols for the synthesis of these extraordinary biomimetic materials and identify critical aspects as well as advantages and disadvantages of different approaches. Furthermore, modifications of established standard procedures are reviewed and discussed with respect to their benefit for the control over morphogenesis and the reproducibility of the experiments in both cases. Finally, we describe currently used techniques for the characterization of these fascinating structures and devise promising ways to analyze their growth behavior and formation mechanisms in situ and as a function of time.