Beyond single-crystal surfaces: The GAL21 water/metal force field.

Solvent effects are notoriously difficult to describe for metallic nanoparticles (NPs). Here, we introduce GAL21 which is the first pairwise additive force field that is specifically designed to modulate the near chemisorption energy of water as a function of the coordination numbers of the metallic atoms. We find a quadratic dependence to be most suitable for capturing the dependence of the adsorption energy of water on the generalized coordination number (GCN) of the metal atoms. GAL21 has been fitted against DFT adsorption energies for Cu, Ag, Au, Ni, Pd, Pt, and Co on 500 configurations and validated on about 3000 configurations for each metal, constructed on five surfaces with GCNs varying from 2.5 to 11.25. Depending on the metals, the root mean square deviation is found between 0.7 kcal mol-1 (Au) to 1.6 kcal mol-1 (Ni). Using GAL21, as implemented in the open-source code CP2K, we then evaluate the solvation energy of Au55 and Pt55 NPs in water using thermodynamic integration. The solvation free energy is found to be larger for Pt than for Au and systematically larger than 200 kcal mol-1, demonstrating the large impact of solvent on the surface energetics of NPs. Still, given that the amorphous NPs are both, the most stable and the most solvated ones, we do not predict a change in the preferred morphology between the gas-phase and in water. Finally, based on a linear regression on three sizes of NPs (from 38 to 147), the solvation energy for Au and Pt surface atoms is found to be -5.2 and -9.9 kcal mol-1, respectively.

Dynamics in the BMIM PF6/acetonitrile mixtures observed by femtosecond optical Kerr effect and molecular dynamics simulations.

We have performed the measurements of the optical Kerr effect signal time evolution up to 4 ns for a mixture of 1-alkyl-3-methyl-imidazolium hexafluorophosphate (BMIM PF6) ionic liquid and acetonitrile in the whole mole fractions range. The long delay line in our experimental setup allowed us to capture the complete reorientational dynamics of the ionic liquid. We have analysed the optical Kerr effect signal in the time and frequency domains with help of molecular dynamics simulations. In our approximation of the slow picosecond dynamics with a multi-exponential decay, we distinguish three relaxation times. The highest two are assigned to the reorientation of the cation and acetonitrile molecules that are in the vicinity of the imidazolium ring. The third one is recognized as originating from cation rotations and reorientation of acetonitrile molecules in the bulk or in the vicinity of the aliphatic chains of the cation. With help of the simulation we interpret the intermolecular band in the reduced spectral density, obtained from Kerr signal, as follows: its low-frequency side results from oscillations of one of the components in the cage formed by its neighbors, while the high-frequency side is attributed to the librations of the cation and acetonitrile molecule as well as the intermolecular oscillations of system components involved in specific interactions. We use this assignment and concentration dependence of the spectra obtained from velocity and angular velocity correlations to explain the mole fraction dependence of Kerr reduced spectral density.