Laser-induced condensation in colloid—polymer mixtures

We study a mixture of hard sphere colloidal particles and non-adsorbing polymers exposed to a plane wave external potential which represents a three-dimensional standing laser field. With computer simulations and density functional theory we investigate the structure and phase behaviour using the simple Asakura-Oosawa model. For varying laser wavelength λ we monitor the emergence of structure in response to the external field, as measured by the amplitude of the oscillations in the one-body density distribution. Between the ideal gas limit for small λ and the bulk limit of large λ there is a non-monotonic crossover that is governed by commensurability of λ and the colloid diameter. The theoretical curves are in good agreement with simulation results. Furthermore, the effect of the periodic field on the liquid-vapour transition is studied, a situation that we refer to as laser-induced condensation. Above a threshold value for λ the theoretical phase diagram indicates the stability of a ‘stacked’ fluid phase, which is a periodic succession (in the beam direction) of liquid and vapour slabs. This partially condensed phase causes a splitting of the liquid-vapour binodal leading to two critical and a triple point. All our predictions should be experimentally observable for colloid-polymer mixtures in an optical resonator.     

31P and 13C chemical shielding tensors in the phosphoenolpyruvate moiety from rotary resonance recoupling 13C and 31P MAS and single crystal 31P NMR

A ³¹P and ¹³C NMR study of powder and single crystal samples of two phosphoenolpyruvate (PEP) compounds, the tris-ammonium salt monohydrate (NH₄)₃(PEP)·H₂O (1), and the mono-ammonium-salt (NH₄)(H₂PEP) (2) is presented. The P chemical shielding tensors in 1 are measured by ³¹P single crystal NMR on four minuscule samples and assigned without ambiguity by exploiting the orientation-dependent ³¹P-³¹p dipolar splittings of the resonance lines. The orientation of the ³¹P chemical shielding tensor is discussed in terms of the C_2v — and C₃-type distortions of the phosphate PO₄-coordination sphere. From ¹³C MAS NMR experiments with ³¹P rotary resonance recoupling on polycrystalline powder samples the orientations of the ³¹P chemical shielding tensors in 1 and 2 are obtained, for 1 in very good agreement with the ³¹P single crystal NMR results. Only some of the orientational parameters of the three ¹³C chemical shielding tensors in the PEP moiety of 1 could be derived from ¹³C MAS NMR experiments with ³¹P rotary resonance recoupling.     

Statistical mechanics of inhomogeneous model colloid—polymer mixtures

We describe two strategies for tackling the equilibrium statistical mechanics of inhomogeneous colloid—polymer mixtures treated in terms of the simple Asakura—Oosawa—Vrij (AO) model, in which colloid—colloid and colloid—polymer interactions are hard-sphere like, whereas the polymer—polymer interaction is zero (perfectly interpenetrating polymer spheres). The first strategy is based upon integrating out the degrees of freedom of the polymer spheres to obtain an effective one-component Hamiltonian for the colloids. This is particularly effective for small size ratios q = σ_p/σ_c < 0.1547, where σ_p and σ_c are the diameters of colloid and polymer spheres, respectively, since in this regime three and higher body contributions to the effective Hamiltonian vanish. In the second strategy we employ a geometry based density functional theory (DFT), specifically designed for the AO model but based on Rosenfeld's fundamental measure DFT for additive mixtures of hard-spheres, that treats colloid and polymer on an equal footing and which accounts for the fluid-fluid phase separation occurring for larger values of q. Using the DFT we investigate the properties of the ‘free’ interface between colloid-rich (liquid) and colloid-poor (gas) fluid phases and adsorption phenomena at the interface between the AO mixture and a hard-wall, for a wide range of size ratios. In particular, for q = 0.6 to 1.0, we find rich interfacial phenomena, including oscillatory density profiles at the free interface and novel wetting and layering phase transitions at the hard-wall-colloid gas interface. Where appropriate we compare our DFT results with those from computer simulations and experiment. We outline several very recent extensions of the basic AO model for which geometry based DFTs have also been developed. These include a model in which the effective polymer sphere—polymer sphere interaction is treated as a repulsive step function rather than ideal and one in which the depletant is a fluid of infinitely thin rods (needles) with orientational degrees of freedom rather than (non-interacting) polymer spheres. We comment on the differences between results obtained from these extensions and those of the basic AO model. Whilst the interfacial properties of the AO model share features in common with the those of simple (atomic) fluids, with the polymer reservoir density replacing the inverse temperature, we emphasize that there are important differences which are related to the many-body character of the effective one-component Hamiltonian.     

MANAGING THE CLIMATE RENT: HOW CAN REGULATORS IMPLEMENT INTERTEMPORALLY EFFICIENT MITIGATION POLICIES?

This paper provides a formal framework to analyze informational and commitment requirements of several intertemporal price and quantity instruments for mitigating global warming. We ask under what conditions and to what extend the regulator can shift the complex and daunting intertemporal optimization of fossil resource use to markets. Mitigation always generates an intertemporal climate rent which reflects the stock‐dependent damages and emerging scarcities of the atmospheric carbon deposit. In order to calculate and to manage this climate rent appropriately, common policy instruments like Pigouvian taxes or emissions trading presume perfect information about resource demand, extraction costs, reserve sizes, and damages for the entire planning horizon. To reduce these informational requirements we develop an alternative policy approach—a state dependent tax rule—that relies only on current observations of cumulative extraction (or atmospheric carbon concentration). Within a cost–benefit analysis, this instrument is capable to shift the complex intertemporal optimization problem completely to the resource sector when resource owners are homogeneous. Under a cost‐effective carbon budget approach, emissions trading with banking and borrowing can also unburden the regulator from solving the intertemporal social planner optimization problem. Additionally, we discuss which instruments can obtain an optimal allocation even if resource owners employ discount rate mark‐ups (i.e., due to imperfect commitment or insecure property rights). While an emissions trading scheme without banking and borrowing is robust against discount rate mark‐ups, resource taxes have to be modified in order to achieve an optimal allocation.     

Anharmonic force field for methanol

An ab initio quartic anharmonic force field for methanol has been calculated at the equilibrium position using the CCSD(T) method for the structure and the harmonic potential energy surface, and the MP4(SDQ) method for the anharmonic part of the surface. A triple zeta basis set was employed with symmetrized curvilinear internal valence coordinates in all calculations. The internal coordinate force field constants have been transformed into force constants in the dimensionless normal coordinate representation for various isotopomers. Vibrational term values for CH₃OH, CH₃OD, CD₃OH, and CD₃OD have been obtained using second order perturbation theory. Particular care has been devoted to the inclusion of Fermi resonance interactions between different vibrational states. A good accuracy has been achieved in the calculation of the fundamentals for all the isotopomers, the mean absolute error being 5.8 cm^?1.     

Hard body amphiphiles at a hard wall

We investigate the structure of amphiphilic molecules exposed to a substrate that is modelled by a hard wall. Our simple model amphiphiles consist of a hard sphere head group to which a vanishingly thin needle tail is radially attached, resulting in a lollipop shape. Such particles act as amphiphiles when added to a binary fluid of hard spheres and needles. Focusing on the pure amphiphile system we compare the results for the positional and orientational order profiles obtained from a recent density functional approximation to those of our computer simulations and find good agreement. For low densities the structure is ruled by the loss of orientational free volume near the wall, while for higher densities packing of the spherical heads dominates. Furthermore, we test the wall sum rule explicitly for this model fluid and find rich structure of the contact distribution which can be interpreted in terms of typical particle configurations.     

NOESY around the critical point ωτc = 1.12. Precise determination of proton-proton distances and reorientation correlation times with two-field NOESY

When nuclear Overhauser enhancement spectroscopy (NOESY) experiments are performed around the critical point ωτ_c = 1.12, internuclear cross-relaxation rates are dependent on the resonance frequency ω, where τ_c is the reorientation time of the distance vector between two magnetic dipoles. Therefore, the correlation times and, consequently, the internuclear distances can be determined precisely by measuring the cross-relaxation rates under two magnetic fields. An application with a cyclic pentapeptide is given as an example, demonstrating the use of the two-field NOESY method in molecular structure studies. NOESY experiments with mixing times beyond 500 ms are discussed.     

Production of electroweak bosons at colliders

The collider experiments at the Tevatron and LHC are accumulating samples of electroweak bosons of unprecedented size. These huge samples can be used to observe rare processes, such as diboson production which have the potential to show enhancements due to new physics. Alternatively, the great statistical power of the samples allows for detailed studies of electroweak production mechanisms and correspondingly QCD and the proton structure.