A topological study of chemical bonds under pressure: solid hydrogen as a model case.

It is now well recognized that a fundamental understanding of the rules that govern chemistry under pressure is still lacking. Hydrogen being the "simplest" element as well as a central core to high pressure physics, we undertake a general study of the changes in the chemical bonding under pressure. We start from a simple trimer unit that has been found in high pressure phases, whose behavior has been found to reveal the basics of hydrogen polymerization under pressure.

Binding of Thioflavin T and Related Probes to Polymorphic Models of Amyloid-β Fibrils.

Alzheimer's disease is a challenge of the utmost importance for contemporary society. An early diagnosis is essential for the development of treatments and for establishing a network of support for the patient. In this light, the deposition in the brain of amyloid-β fibrillar aggregates, which is a distinctive feature of Alzheimer, is key for an early detection of this disease.

Decoupling the Effects of Mass Density and Hydrogen-, Oxygen-, and Aluminum-Based Defects on Optoelectronic Properties of Realistic Amorphous Alumina.

The search for functional materials is currently hindered by the difficulty to find significant correlation between constitutive properties of a material and its functional properties. In the case of amorphous materials, the diversity of local structures, chemical composition, impurities and mass densities makes such a connection difficult to be addressed. In this Letter, the relation between refractive index and composition has been investigated for amorphous AlO materials, including nonstoichiometric AlO, emphasizing the role of structural defects and the absence of effect of the band gap variation.

Microhydration of Protonated Nα-Acetylhistidine: A Theoretical Approach.

Extensive exploration of the potential energy surfaces of protonated Nα-acetylhistidine hydrated by 0-3 molecules of water was performed. The methodology combined hierarchical and genealogical (Darwin family tree) approaches using polarizable AMOEBA force field and M06 functional. It is demonstrated that this mixed approach allows recovering a larger number of conformers than the number recovered by using any one of the two methods alone.

Benchmarking DFT and TD-DFT Functionals for the Ground and Excited States of Hydrogen-Rich Peptide Radicals.

We assess the pros and cons of a large panel of DFT exchange-correlation functionals for the prediction of the electronic structure of hydrogen-rich peptide radicals formed after electron attachment on a protonated peptide. Indeed, despite its importance in the understanding of the chemical changes associated with the reduction step, the question of the attachment site of an electron and, more generally, of the reduced species formed in the gas phase through electron-induced dissociation (ExD) processes in mass spectrometry is still a matter of debate. For hydrogen-rich peptide radicals in which several positive groups and low-lying π* orbitals can capture the incoming electron in ExD, inclusion of full Hartree-Fock exchange at long-range interelectronic distance is a prerequisite for an accurate description of the electronic states, thereby excluding several popular exchange-correlation functionals, e.

Gas-phase structures and thermochemistry of neutral histidine and its conjugated acid and base.

Extensive exploration of the conformational space of neutral, protonated and deprotonated histidine has been conducted at the G4MP2 level. Theoretical protonation and deprotonation thermochemistry as well as heats of formation of gaseous histidine and its ionized forms have been calculated at the G4 level considering either the most stable conformers or an equilibrium population of conformers at 298 K. These theoretical results were compared to evaluated experimental determinations.

Acid-base thermochemistry of gaseous oxygen and sulfur substituted amino acids (Ser, Thr, Cys, Met).

Acid-base thermochemistry of isolated amino acids containing oxygen or sulfur in their side chain (serine, threonine, cysteine and methionine) have been examined by quantum chemical computations. Density functional theory (DFT) was used, with B3LYP, B97-D and M06-2X functionals using the 6-31+G(d,p) basis set for geometry optimizations and the larger 6-311++G(3df,2p) basis set for energy computations. Composite methods CBS-QB3, G3B3, G4MP2 and G4 were applied to large sets of neutral, protonated and deprotonated conformers.