Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Identifying and quantifying nonconservative energy production/destruction terms in hydrostatic Boussinesq primitive equation models

This paper seeks to illustrate the point that physical inconsistencies between thermodynamics and dynamics usually introduce nonconservative production/destruction terms in the local total energy balance equation in numerical ocean general circulation models (OGCMs). Such terms potentially give rise to undesirable forces and/or diabatic terms in the momentum and thermodynamic equations, respectively, which could explain some of the observed errors in simulated ocean currents and water masses. In this paper, a theoretical framework is developed to provide a practical method to determine such nonconservative terms, which is illustrated in the context of a relatively simple form of the hydrostatic Boussinesq primitive equation used in early versions of OGCMs, for which at least four main potential sources of energy nonconservation are identified; they arise from: (1) the “hanging” kinetic energy dissipation term; (2) assuming potential or conservative temperature to be a conservative quantity; (3) the interaction of the Boussinesq approximation with the parameterizations of turbulent mixing of temperature and salinity; (4) some adiabatic compressibility effects due to the Boussinesq approximation. In practice, OGCMs also possess spurious numerical energy sources and sinks, but they are not explicitly addressed here. Apart from (1), the identified nonconservative energy sources/sinks are not sign definite, allowing for possible widespread cancellation when integrated globally. Locally, however, these terms may be of the same order of magnitude as actual energy conversion terms thought to occur in the oceans. Although the actual impact of these nonconservative energy terms on the overall accuracy and physical realism of the oceans is difficult to ascertain, an important issue is whether they could impact on transient simulations, and on the transition toward different circulation regimes associated with a significant reorganization of the different energy reservoirs. Some possible solutions for improvement are examined. It is thus found that the term (2) can be substantially reduced by at least one order of magnitude by using conservative temperature instead of potential temperature. Using the anelastic approximation, however, which was initially thought as a possible way to greatly improve the accuracy of the energy budget, would only marginally reduce the term (4) with no impact on the terms (1), (2) and (3).

Transition metal clusters on graphite

The topic of this work is 3d transition metals deposited on graphite. Spin-polarised density-functional calculations are used to obtain the magnetic moments of deposited adatoms and dimers. Interatomic potentials are also deduced. These are used in molecular dynamics simulations to study cluster formation and to investigate cluster morphology.

Dynamic data reconciliation for sequential modular simulators: application to a mixing process

This paper describes a method for dynamic data reconciliation of nonlinear systems that are simulated using the sequential modular approach, and where individual modules are represented by a class of differential algebraic equations. The estimation technique consists of a bank of extended Kalman filters that are integrated with the modules. The paper reports a study based on experimental data obtained from a pilot scale mixing process.

Rigid ferrocenophane and its metal complexes with transition and alkaline-earth metal ions

The rigid [6]ferrocenophane, L-1, was synthesised by condensation of 1,1'-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L-2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L-1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L-1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M (Bu4NPF6)-Bu-n as the supporting electrolyte. The electrochemical process of L-1 between 300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc(+) wave of L-1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L-1 weak interactions and they promote the acid-base equilibrium of L-1. This reveals that L-1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [(PdLCl2)-Cl-1] was determined and showed a square-planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) angstrom. The experimental anodic shifts were elucidated by DFT calculations on the [(MLCl2)-Cl-1] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.

Remote forcing of the Antarctic Circumpolar Current by diapycnal mixing

We show that diapycnal mixing can drive a significant Antarctic Circumpolar Current (ACC) volume transport, even when the mixing is located remotely in northern-hemisphere ocean basins. In the case of remote forcing, the globally-averaged diapycnal mixing coefficient is the important parameter. This result is anticipated from theoretical arguments and demonstrated in a global ocean circulation model. The impact of enhanced diapycnal mixing on the ACC during glacial periods is discussed.

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using latticebased Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.