The interfaces formed between a zinc-terminated polar zinc oxide (0002) surface and a series of chemisorbed fluorinated benzylphosphonic acids have been studied at the density functional theory level. The results indicate that there occur substantial changes in the adsorption energy and surface work function whether the binding mode is bidentate or tridentate. Also, the trends and magnitude of the various factors that determine the total modifications in work function markedly vary between the two binding modes. We have also calculated the oxygen core-level binding energy shifts of the PO 3 moiety with respect to the oxygen atoms in bulk ZnO; good agreement is obtained between the calculated values of the core-level binding energy shifts for the tridentate binding mode and available X-ray photoelectron spectroscopy data.

In this work, we present infrared (IR) spectra of H7O3(+) and its deuterium isotopomers calculated by direct molecular dynamics (MD) simulations at the B3LYP/6-31+G** computational level. The calculated spectra obtained at 100, 300, and 500 K were compared to available experimental observations, and spectral features were assigned using normal-mode analysis (NMA) and driven molecular dynamics (DMD). Spectral peaks at 2410 and 2540 cm(-1) were assigned to asymmetric and symmetric stretches of the bridging hydrogen (BH) using NMA. The weak spectral features at 2166 and 2275 cm(-1) were assigned to a combination band of BH asymmetric stretch, H2O in phase wagging, OO stretch, and H3O(+) rocking vibrations by DMD simulations. Our observation of BH stretch vibrations as low as 2166 cm(-1) is in good agreement with the assignment of the low-resolution spectrum obtained by Schwarz at 2200-2300 cm(-1) [Schwarz, H. A. J. Chem. Phys. 1977, 67, 5525-5534] and vibrational predissociation spectrum by Lee et al. ∼2300 cm(-1) [Okumura, M.; Yeh, L. I.; Myers, J. D.; Lee, Y. T. J. Chem. Phys. 1990, 94, 3416-3427].

We have characterized theoretically the work-function modifications of the (111) surfaces of gold and silver upon deposition of self-assembled monolayers based on methanethiol and trifluoromethanethiol. A comparative analysis is made between the experimental results and those obtained from two widely used approaches based on density functional theory. The contributions to the total work-function modifications are estimated on the basis of two decomposition schemes of the thiol molecules that have been proposed in the literature. The contributions are found to differ significantly between the two approaches, as do the corresponding adsorption energies.

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