Assessing the effect of a liquid water layer on the adsorption of hydrate anti-agglomerants using molecular simulations.

We have performed molecular dynamics simulations to study the adsorption of ten hydrate anti-agglomerants onto a mixed methane-propane sII hydrate surface covered by layers of liquid water of various thickness. As a general trend, we found that the more liquid water that is present on the hydrate surface, the less favorable the adsorption becomes even though there are considerable differences between the individual molecules, indicating that the presence and thickness of this liquid water layer are crucial parameters for anti-agglomerant adsorption studies. Additionally, we found that there exists an optimal thickness of the liquid water layer favoring hydrate growth due to the presence of both liquid water and hydrate-forming guest molecules. For all other cases of liquid water layer thickness, hydrate growth is slower due to the limited availability of hydrate-forming guests close to the hydrate formation front. Finally, we investigated the connection between the thickness of the liquid water layer and the degree of subcooling and found a very good agreement between our molecular dynamics simulations and theoretical predictions.

Structural Effects of Gas Hydrate Antiagglomerant Molecules on Interfacial Interparticle Force Interactions.

Gas hydrate interparticle cohesive forces are important to determine the hydrate crystal particle agglomeration behavior and subsequent hydrate slurry transport that is critical to preventing potentially catastrophic consequences of subsea oil/gas pipeline blockages. A unique high-pressure micromechanical force apparatus has been employed to investigate the effect of the molecular structure of industrially relevant hydrate antiagglomerant (AA) inhibitors on gas hydrate crystal interparticle interactions. Four AA molecules with known detailed structures [quaternary ammonium salts with two long tails (R1) and one short tail (R2)] in which the R1 has 12 carbon (C12) and 8 carbon (C8) and saturated (C-C) versus unsaturated (C═C) bonding are used in this work to investigate their interfacial activity to suppress hydrate crystal interparticle interactions in the presence of two liquid hydrocarbons (n-dodecane and n-heptane). All AAs were able to reduce the interparticle cohesive force from the baseline (23.5 ± 2.5 mN m-1), but AA-C12 shows superior performance in both liquid hydrocarbons compared to the other AAs. The interfacial measurements indicate that the AA with an R1 longer alkyl chain length can provide a denser barrier, and the AA molecules may have higher packing density when the AA R1 alkyl tail length is comparable to that of the liquid hydrocarbon chain on the gas hydrate crystal surface. Increasing the salinity can promote the effectiveness of an AA molecule and can also eliminate the effect of longer particle contact times, which typically increases the interparticle cohesive force. This work reports the first experimental investigation of high-performance known molecular structure AAs under industrially relevant conditions, showing that these molecules can reduce the interfacial tension and increase the gas hydrate-water contact angle, thereby minimizing the gas hydrate interparticle interactions. The structure-performance relation reported in this work can be used to help in the design of improved AA inhibitor molecules that will be critical to industrial hydrate crystal slurry transport.

Size dependence of the dissociation process of spherical hydrate particles via microsecond molecular dynamics simulations.

The dissociation process of spherical sII mixed methane-propane hydrate particles in liquid hydrocarbon was investigated via microsecond-long molecular dynamics simulations. A strong dependence of the melting temperature on the particle size was found. Analysis in the context of the Gibbs-Thomson effect provided insights into the fundamental properties of gas hydrates.

Paramagnetic Zinc(II) Complexes of a Bis(catechol): Dependence of Product Spin State on Tautomerization of the Bis(catechol) Ligand.

We report the preparation and characterization of zinc(II) hydrotris(3-cumenyl-5-methylpyrazolyl)borate (LZn) complexes, (LZn)(2)()1'-H and (LZn)(2)()1, of a bis(catechol) ligand. The formation of (LZn)(2)()1'-H, an S = (1)/(2) complex, rather than (LZn)(2)()1, an S = 1 complex, is observed due to tautomerization of a reaction intermediate. The biradical complex, (LZn)(2)()1, can be prepared from (LZn)(2)()1'-H by oxidation, a conversion that is accompanied by a blue-green to red-purple color change and an increase in spin from (1)/(2) to 1. The frozen solution EPR spectrum of the biradical complex (LZn)(2)()1 exhibits zero-field splitting and a Deltam(s)() = 2 transition characteristic of a triplet state. The temperature dependence of the EPR signal intensity is consistent with high-spin coupling of the unpaired electrons of the ligand.

Singlet-triplet gap in triplet ground-state biradicals is modulated by substituent effects.

Three S = 1 bis(semiquinone) complexes have been prepared. To ensure ferromagnetic intramolecular exchange coupling, the two semiquinones are attached 1,3 to a 5-substituted phenylene ring. The biradical complexes differ in their meta-substituents: 1-NMe(2)(), X = N,N-dimethylamino; 1-t-Bu, X = tert-butyl; 1-NO(2)(), X = nitro. All three structures have been determined by X-ray crystallography. Results of structural studies indicate that the biradical ligands of all three complexes have nearly identical conformations with average semiquinone ring torsions of 32 degrees +/- 2 degrees relative to the 5-substituted phenylene ring. The exchange parameter, J (Eta = -2JS(1).S(2)), ranges from +31.0 +/- 0.6 cm(-)(1) for 1-NO(2)() to +59.3 +/- 1.2 cm(-)(1) for 1-t-Bu, with J = +34.9 +/- 0.7 cm(-)(1) for 1-NMe(2)(). Since the conformations are nearly identical, the differences in exchange coupling parameter J are due to substituent effects. The experimental results are supported by Hückel theory arguments and previous computational work.

Trends in metal-biradical exchange interaction for first-row M(II)(nitronyl nitroxide-semiquinone) complexes.

We report molecular structures and temperature-dependent magnetic susceptibility data for several new metal complexes of heterospin triplet ground-state biradical ligands. The ligands are comprised of both nitronyl-nitroxide (NN) and semiquinone (SQ) spin carriers. Five compounds are five-coordinate M(II) complexes (M = Mn, Co, Ni, Cu, and Zn), and one is a six-coordinate Ni(II) complex. Five compounds were structurally characterized. During copper complex formation a reaction with methanol occurs to form a unique methoxy-substituted SQ ring. Variable-temperature magnetic susceptibility studies are consistent with strong intraligand (NN-SQ and NN-PhSQ) ferromagnetic exchange coupling. For the five-coordinate Mn, Co, and Ni complexes, the S = 1 ligand is antiferromagnetically coupled to the metal. For both the five-coordinate Cu complex and the six-coordinate Ni complex, the ligand is ferromagnetically coupled to the metal spins in accordance with orbital symmetry arguments. Despite the low molecular symmetries, the predicted trend in metal-ligand exchange interactions is supported by spin dimer analysis based on extended Hückel calculations. For (NN-SQ)NiTp(Cum,Me)() (Tp(Cum,Me)() = hydro-tris(3-cumenyl-5-methylpyrazolyl)borate), an antisymmetric exchange term was required for the best fit of the magnetic susceptibility data. Antisymmetric exchange was less important for the other complexes due to inherently smaller Deltag. Finally, it is shown that intraligand exchange coupling is of paramount importance in stabilizing high-spin states of mixed metal-biradical complexes.

Trends in exchange coupling for trimethylenemethane-type Bis(semiquinone) biradicals and correlation of magnetic exchange with mixed valency for cross-conjugated systems.

A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states.