Solvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid‐phase catalysts. Thus, it is important to... Show moreSolvation can significantly modify the adsorption energy of species at surfaces, thereby influencing the performance of electrocatalysts and liquid‐phase catalysts. Thus, it is important to understand adsorbate solvation at the nanoscale. Here we evaluate the effect of van der Waals (vdW) interactions described by different approaches on the solvation energy of *OH adsorbed on near‐surface alloys (NSAs) of Pt. Our results show that the studied functionals can be divided into two groups, each with rather similar average *OH solvation energies: (1) PBE and PW91; and (2) vdW functionals, RPBE, PBE‐D3 and RPBE‐D3. On average, *OH solvation energies are less negative by ∼0.14 eV in group (2) compared to (1), and the values for a given alloy can be extrapolated from one functional to another within the same group. Depending on the desired level of accuracy, these concrete observations and our tabulated values can be used to rapidly incorporate solvation into models for electrocatalysis and liquid‐phase catalysis. Show less
Govindarajan, N.; Koper, M.T.M.; Meijer, E.J.; Calle-Vallejo, F. 2019
A structural characterization of the products formed in the dissociative electron ionization of adamantane (C10H16) is presented. Molecular structures of product ions are suggested based on... Show moreA structural characterization of the products formed in the dissociative electron ionization of adamantane (C10H16) is presented. Molecular structures of product ions are suggested based on multiple‐photon dissociation spectroscopy using the Free Electron Laser for Infrared eXperiments (FELIX) in combination with quantum‐chemical calculations. Product ions are individually isolated in an ion trap tandem mass spectrometer and their action IR spectra are recorded. Atomic hydrogen loss from adamantane yields the 1‐adamantyl isomer. The IR spectrum of the C8H11+ product ion is best reproduced by computed spectra of 2‐ and 4‐protonated meta‐xylene and ortho‐ and para‐protonated ethylbenzenes. The spectrum of the product ion at m/z 93 suggests that it is composed of a mixture of ortho‐protonated toluene, para‐protonated toluene and 1,2‐dihydrotropylium, while the spectrum of the m/z 79 ion is consistent with the benzenium ion. This study thus suggests that adamantane is efficiently converted into aromatic species and astrophysical implications for the interstellar medium are highlighted. Show less
Briquet, L.G.V.; Sarwar, M.; Mugo, J.; Jones, G.; Calle Vallejo, F. 2017
