Covalent bond shortening and distortion induced by pressurization of thorium, uranium, and neptunium tetrakis aryloxides.

Covalency involving the 5f orbitals is regularly invoked to explain the reactivity, structure and spectroscopic properties of the actinides, but the ionic versus covalent nature of metal-ligand bonding in actinide complexes remains controversial. The tetrakis 2,6-di-tert-butylphenoxide complexes of Th, U and Np form an isostructural series of crystal structures containing approximately tetrahedral MO cores. We show that up to 3 GPa the Th and U crystal structures show negative linear compressibility as the OMO angles distort.

Contrasting behaviour under pressure reveals the reasons for pyramidalization in tris(amido)uranium(III) and tris(arylthiolate) uranium(III) molecules.

A range of reasons has been suggested for why many low-coordinate complexes across the periodic table exhibit a geometry that is bent, rather a higher symmetry that would best separate the ligands. The dominating reason or reasons are still debated. Here we show that two pyramidal UX molecules, in which X is a bulky anionic ligand, show opposite behaviour upon pressurisation in the solid state.

Effect of ammonium fluoride doping on the ice III to ice IX phase transition.

Ice III is a hydrogen-disordered phase of ice that is stable between about 0.2 and 0.35 GPa.

Quantum chemical topology and natural bond orbital analysis of M-O covalency in M(OCH) (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np).

Covalency is complex yet central to our understanding of chemical bonding, particularly in the actinide series. Here we assess covalency in a series of isostructural d and f transition element compounds M(OCH) (M = Ti, Zr, Hf, Ce, Th, Pa, U, Np) using scalar relativistic hybrid density functional theory in conjunction with the Natural Bond Orbital (NBO), quantum theory of atoms in molecules (QTAIM) and interacting quantum atoms (IQA) approaches. The IQA exchange-correlation covalency metric is evaluated for the first time for actinides other than uranium, in order to assess its applicability in the 5f series.

Amorphous Mixtures of Ice and C Fullerene.

Carbon and ice make up a substantial proportion of our universe. Recent space exploration has shown that these two chemical species often coexist such as on comets and asteroids and in the interstellar medium. Here, we prepare mixtures of C fullerene and HO by vapor codeposition at 90 K with molar C/HO ratios ranging from 1:1254 to 1:5.

Gaseous "nanoprobes" for detecting gas-trapping environments in macroscopic films of vapor-deposited amorphous ice.

Vapor-deposited amorphous ice, traditionally called amorphous solid water (ASW), is one of the most abundant materials in the universe and a prototypical material for studying physical vapor-deposition processes. Its complex nature arises from a strong tendency to form porous structures combined with complicated glass transition, relaxation, and desorption behavior. To gain further insights into the various gas-trapping environments that exist in ASW and hence its morphology, films in the 25-100 μm thickness range were codeposited with small amounts of gaseous "nanoprobes" including argon, methane, helium, and carbon dioxide.

Computational analysis of M-O covalency in M(OCH) (M = Ti, Zr, Hf, Ce, Th, U).

A series of compounds M(OC6H5)4 (M = Ti, Zr, Hf, Ce, Th, U) is studied with hybrid density functional theory, to assess M-O bond covalency. The series allows for the comparison of d and f element compounds that are structurally similar. Two well-established analysis methods are employed: Natural Bond Orbital and the Quantum Theory of Atoms in Molecules.

2D IR spectroscopy of high-pressure phases of ice.

We present experimental and simulated 2D IR spectra of some high-pressure forms of isotope-pure DO ice and compare the results to those of ice Ih published previously [F. Perakis and P. Hamm, Phys.

Is High-Density Amorphous Ice Simply a "Derailed" State along the Ice I to Ice IV Pathway?

The structural nature of high-density amorphous ice (HDA), which forms through low-temperature pressure-induced amorphization of the "ordinary" ice I, is heavily debated. Clarifying this question is important for understanding not only the complex condensed states of HO but also in the wider context of pressure-induced amorphization processes, which are encountered across the entire materials spectrum. We first show that ammonium fluoride (NHF), which has a similar hydrogen-bonded network to ice I, also undergoes a pressure collapse upon compression at 77 K.

Detailed crystallographic analysis of the ice VI to ice XV hydrogen ordering phase transition.

The DO ice VI to ice XV hydrogen ordering phase transition at ambient pressure is investigated in detail with neutron diffraction. The lattice constants are found to be sensitive indicators for hydrogen ordering. The a and b lattice constants contract whereas a pronounced expansion in c is found upon hydrogen ordering.

A new structural relaxation pathway of low-density amorphous ice.

Low-density amorphous (LDA) ice is involved in critical cosmological processes and has gained prominence as one of the at least two distinct amorphous forms of ice. Despite these accolades, we still have an incomplete understanding of the structural diversity that is encompassed within the LDA state and the dynamic processes that take place upon heating LDA. Heating the high-pressure ice VIII phase at ambient pressure is a remarkable example of temperature-induced amorphisation yielding LDA.

Spectroscopic Signature of Stacking Disorder in Ice I.

There is a growing realization that the presence of stacking disorder in ice I strongly influences its physical and chemical properties. Using Raman spectroscopy, we gain new fundamental insights into the spectroscopic properties of ice. We show that stacking disorder can be detected and quantified by comparing the spectra of stacking disordered ice with spectra of the "ordinary" hexagonal ice Ih.

Salt modulates bacterial hydrophobicity and charge properties influencing adhesion of Pseudomonas aeruginosa (PA01) in aqueous suspensions.

The influence on cell hydrophobicity of differential extension with ionic strength of lipopolysaccharide molecules (LPS), which exist as charged and uncharged polymers at the surface of the gram-negative bacterium Pseudomonas aeruginosa (PA01), has been investigated. Attenuated total reflection infrared (ATR-IR) spectral absorptions from a single layer of cells adsorbed to ZnSe increased in intensity with increasing NaCl concentration up to 0.1 mol L(-1).

Structure and conformation of methyl-terminated poly(ethylene oxide)-bis[methylenephosphonate] ligands adsorbed to boehmite (AlOOH) from aqueous solutions. Attenuated total reflection infrared (ATR-IR) spectra and dynamic contact angles.

A ligand with a bisphosphonate headgroup and methyl-terminated poly(ethylene oxide) 550 tail has been adsorbed to a boehmite (AlOOH) particle film from aqueous solutions at 9, 18, 26, and 40 degrees C with a range of coverages. In situ attenuated total reflectance infrared (ATR-IR) spectra of the PEO-modified boehmite particle films has been used to monitor surface coverage. PEO-related IR absorptions showed variation in band shape with coverage and temperature which reflect changes in the configuration and crowding of PEO ligand tails.

Structure and conformation in mixtures of methyl-terminated poly(ethylene oxide) and water. Principal component analysis and band fitting of infrared absorptions.

Infrared absorption spectra of aqueous mixtures of poly(ethylene oxide) dimethyl ether (PEO), with a number average molecular weight of 500 and a water volume fraction between 0 and 0.96 have been recorded at 18, 26, and 40 degrees C. Composition and temperature were found to influence the intensity and wavenumber of PEO-related absorptions.