Macroscopic modelling of the surface tension of polymer-surfactant systems

Polymer-surfactant mixtures are increasingly being used in a wide range of applications. Weakly-interacting systems, such as SDS/PEO and SDS/PVP, comprise ionic surfactants and neutral polymers, while strongly-interacting systems, such as SDS/POLYDMDAAC and C12TAB/NaPSS, comprise ionic surfactants and oppositely charged ionic polymers. The complex nature of interactions in the mixtures leads to interesting and surprising surface tension profiles as the concentrations of polymer and surfactant are varied. The purpose of our research has been to develop a model to explain these surface tension profiles and to understand how they relate to the formation of different complexes in the bulk solution. In this paper we shouw how an existing model based on the law of mass action can be extended to model the surface tension of weakly-interacting systems, and we also extend it further to produce a model for the surface tension of strongly interacting systems. Applying the model to a variety of strongly-interacting systems gives remarkable agreement with the experimental results. The model provides a sound theoretical basis for comparing and contrasting the behaviour of different systems and greatly enhances our understanding of the features observed

Spin-Vibronic Intersystem Crossing and Molecular Packing Effects in Heavy Atom Free Organic Phosphor.

We present a detailed investigation into the excited state properties of a planar symmetric azatriangulenetrione, HTANGO, which has received significant interest due to its high solid-state phosphorescence quantum yield and therefore potential as an organic room temperature phosphorescent (ORTP) dye. Using a model linear vibronic coupling Hamiltonian in combination with quantum dynamics simulations, we observe that intersystem crossing (ISC) in HTANGO occurs with a rate of ∼10 s , comparable to benzophenone, an archetypal molecule for fast ISC in heavy metal free molecules. Our simulations demonstrate that the mechanism for fast ISC is associated with the high density of excited triplet states which lie in close proximity to the lowest singlet states, offering multiple channels into the triplet manifold facilitating rapid population transfer. Finally, to rationalize the solid-state emission properties, we use quantum chemistry to investigate the excited state surfaces of the HTANGO dimer, highlighting the influence and importance of the rotational alignment between the two HTANGO molecules in the solid state and how this contributes to high phosphorescence quantum yield

Hydrophobicity with atomic resolution: Steady-state and ultrafast X-ray absorption and molecular dynamics studies

Static and time-resolved X-ray absorption spectroscopy (XAS) is used to probe the solvent shell structure around iodide and iodine. In particular, we characterize the changes observed upon electron abstraction of aqueous iodide, which reflects the transition from hydrophilic to hydrophobic solvation after impulsive electron abstraction from iodide. The static spectrum of aqueous iodide, which is analyzed using quantum mechanical/molecular mechanics (QM/MM) molecular dynamics (MD) simulations, indicates that the hydrogens of the closest water molecules point toward the iodide, as expected for hydrophilic solvation. In addition, these simulations demonstrate a small anisotropy in the solvent shell. Following electron abstraction, most of the water molecules move away from iodine, while one comes closer to form a complex with it that survives for 3-4 ps. This lifetime is governed by the reorganization of the main solvation shell, basically the time it takes for the water molecules to reform a hydrogen bond network in the hydrophobic solvation shel

Effect of <i>tert</i>-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-<i>N</i>-Heterocyclic Carbene Complex

Understanding and subsequently being able to manipulate the excited-state decay pathways of functional transition-metal complexes is of utmost importance in order to solve grand challenges in solar energy conversion and data storage. Herein, we perform quantum chemical calculations and spin-vibronic quantum dynamics simulations on the Fe-<i>N</i>-heterocyclic carbene complex, [Fe­(btbip)₂]²⁺ (btbip = 2,6-bis­(3-<i>tert</i>-butyl-imidazole-1-ylidene)­pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe­(bmip)₂]²⁺ (bmip = 2,6-bis­(3-methyl-imidazole-1-ylidene)­pyridine), completely alters the excited-state relaxation. Ultrafast deactivation of the initially excited metal-to-ligand charge transfer (^1,3MLCT) states occurs within 350 fs. In contrast to the widely adopted mechanism of Fe­(II) photophysics, these states decay into close-lying singlet metal-centered (¹MC) states. This occurs because the <i>tert</i>-butyl functionalization stabilizes the ¹MC states, enabling the ^1,3MLCT → ¹MC population transfer to occur close to the Franck–Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet and quintet MC states. These results will inspire highly involved ultrafast experiments performed at X-ray free electron lasers and shall pave the way for the design of novel high-efficiency transition-metal-based functional molecules

Ultrafast core-loss spectroscopy in four-dimensional electron microscopy

We demonstrate ultrafast core-electron energy-loss spectroscopy in four-dimensional electron microscopy as an element-specific probe of nanoscale dynamics. We apply it to the study of photoexcited graphite with femtosecond and nanosecond resolutions. The transient core-loss spectra, in combination with ab initio molecular dynamics simulations, reveal the elongation of the carbon-carbon bonds, even though the overall behavior is a contraction of the crystal lattice. A prompt energy-gap shrinkage is observed on the picosecond time scale, which is caused by local bond length elongation and the direct renormalization of band energies due to temperature-dependent electron–phonon interactions

The kinetics of surfactant desorption at the air–solution interface

The kinetics of desorption of the anionic surfactant sodium dodecylbenzene sulfonate at the air–solution interface have been studied using neutron reflectivity (NR). The experimental arrangement incorporates a novel flow cell in which the subphase can be exchanged (diluted) using a laminar flow whilst the surface region remains unaltered. The kinetics of the desorption is relatively slow and occurs over many tens of minutes compared with the dilution timescale of approximately 10–30 minutes. A detailed mathematical model, in which the rate of the desorption is determined by transport through a near-surface diffusion layer into a diluted bulk solution below, is developed and provides a good description of the timedependent adsorption data.\ud \ud A key parameter of the model is the ratio of the depth of the diffusion layer, Hc , to the depth of the fluid, Hf, and we find that this is related to the reduced Péclet number, Pe*, for the system, via Hc/Hf, = C/Pe* 1/ 2 . Although from a highly idealised experimental arrangement, the results provide an important insight into the ‘rinse mechanism’, which is applicable to a wide variety of domestic and industrial circumstances