From Gold Nanoseeds to Nanorods: The Microscopic Origin of the Anisotropic Growth

Directly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic growth with the less protected tips growing faster. When silver salt is added to the growth solution, the asymmetry of the facets is preserved, but the Br^? concentration at the interface increases, resulting in increased surface passivation.     

Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, 'ice-like' and 'liquid-like' features in these spectra are interpreted as the result of hydrogen bonds of different strengths between surface silanols/aluminols and water.     

Surface Charges at the CaF2/Water Interface Allow Very Fast Intermolecular Vibrational‐Energy Transfer

We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface‐specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D₂O) molecules and provide information about the sub‐picosecond vibrational‐energy‐relaxation dynamics at the buried solid/liquid interface. We find that strongly H‐bonded OD groups, with a vibrational frequency below 2500 cm^?1, display very rapid spectral diffusion and vibrational relaxation; for weakly H‐bonded OD groups, above 2500 cm^?1, the dynamics slows down substantially. Atomistic simulations based on electronic‐structure theory reveal the molecular origin of energy transport through the local H‐bond network. We conclude that strongly oriented H‐bonded water molecules in the adsorbed layer, whose orientation is pinned by the localized charge defects, can exchange vibrational energy very rapidly due to the strong collective dipole, compensating for a partially missing solvation shell.     

The oxidation of tyrosine and tryptophan studied by a molecular dynamics normal hydrogen electrode

The thermochemical constants for the oxidation of tyrosine and tryptophan through proton coupled electron transfer in aqueous solution have been computed applying a recently developed density functional theory (DFT) based molecular dynamics method for reversible elimination of protons and electrons. This method enables us to estimate the solvation free energy of a proton (H(+)) in a periodic model system from the free energy for the deprotonation of an aqueous hydronium ion (H(3)O(+)). Using the computed solvation free energy of H(+) as reference, the deprotonation and oxidation free energies of an aqueous species can be converted to pK(a) and normal hydrogen electrode (NHE) potentials. This conversion requires certain thermochemical corrections which were first presented in a similar study of the oxidation of hydrobenzoquinone [J. Cheng, M. Sulpizi, and M. Sprik, J. Chem. Phys. 131, 154504 (2009)]. Taking a different view of the thermodynamic status of the hydronium ion, these thermochemical corrections are revised in the present work. The key difference with the previous scheme is that the hydronium is now treated as an intermediate in the transfer of the proton from solution to the gas-phase. The accuracy of the method is assessed by a detailed comparison of the computed pK(a), NHE potentials and dehydrogenation free energies to experiment. As a further application of the technique, we have analyzed the role of the solvent in the oxidation of tyrosine by the tryptophan radical. The free energy change computed for this hydrogen atom transfer reaction is very similar to the gas-phase value, in agreement with experiment. The molecular dynamics results however, show that the minimal solvent effect on the reaction free energy is accompanied by a significant reorganization of the solvent.     

Acidity constants from vertical energy gaps: density functional theory based molecular dynamics implementation

The question of how to compute acidity constants (pK(a)) treating solvent and solute at the same level of theory remains of some interest, for example in the case of high or low pH conditions. We have developed a density functional theory based molecular dynamics implementation of such a method. The method is based on a half reaction scheme computing free energies of dissociation from the vertical energy gaps for insertion or removal of protons. Finite system size effects are important, but largely cancel when half reactions are combined to full reactions. We verified the method by investigating a series of organic and inorganic acids and bases spanning a wide range of pK(a) values (20 units). We find that the response of the aqueous solvent to vertical protonation/deprotonation is almost always asymmetric and correlated with the strength of the hydrogen bonding of the deprotonated base. We interpret these observations in analogy with the picture of solvent response to electronic ionization.