The adsorption of cyclohexane, benzene, and alkyl-substituted benzene derivatives is studied on rutile TiO2(110) by a combination of molecular beam dosing, temperature-programmed desorption, and density functional theory (DFT). An inversion analysis is used to extract the coverage-dependent desorption energies from TiO2(110). The values of the suitable prefactors are derived from simple statistical mechanical models assuming different limits in the adsorbate mobility on the surface. The prefactor values determined using the vibrational frequencies from DFT calculations corroborate this analysis and show that the adsorbates are mobile in one or two dimensions on a corrugated TiO2(110) surface. The adsorption of benzene derivatives is found to be dominated by the dative Lewis acid–base interactions of the π system with the surface Ti ions. While the desorption energy generally increases with increasing the length and the number of substituents, the difference between the desorption energies decreases as the number and length of substituents are increased. This is a consequence of the destabilization of the optimum bonding configuration of the benzene ring and the alkyl groups with their increasing length and number. The absolute saturation coverages of uncompressed layers correspond approximately to one molecule per three Ti5c sites and decrease slightly with increasing molecule size, in good agreement with van der Waals sizes of the molecules.

Potential energy surfaces for the group 11 trimers were generated at various levels of coupled-cluster theory to examine the effects of Jahn–Teller distortions. Our calculations show that the lowest-energy conformer for Cu3, Ag3, and Au3 is the 2B2 (∼65° isomer) without spin–orbit corrections. Spin–orbit corrections have negligible contributions to the relative energies for the angle dependence of the potential energy surfaces for Cu3 and Ag3. The inclusion of spin–orbit corrections for Au3 makes the 2B2 (∼65°) and 2A1 (∼55°) states approximately degenerate. A novel 2B2 isomer of Au3 at an obtuse angle of ∼125° was also characterized, providing evidence for bond angle isomerism on the same 2B2 potential energy surface. Spin–orbit corrections increase the barrier height between the 2B2 (65°) and 2B2 (125°) bond angle isomers of Au3. The calculated symmetric stretch vibrational frequencies are in good agreement with the available experimental values. All frequencies calculated for the Au3 2B2 (∼125°) state are real, and there is at least one bound bending vibration for this state. Jahn–Teller parameters are also derived for each trimer.

The geometries of the group 11 coinage metals (n = 2−20) were optimized to determine the lowest energy isomers for each cluster size, singlets for even numbers and doublets for odd numbers. For copper and silver, 2-D (planar) geometries were favored up to n = 6. For gold, 2D (planar) geometries were favored up to n = 13. Normalized clustering energies were plotted as a function of cluster size (n −1/3 , for n = 4−20) with various DFT functionals and the CCSD(T)-F12b method and were extrapolated to predict the bulk cohesive energy. In the case of copper and silver, there is excellent agreement between the cohesive energies predicted at the CCSD(T)-F12b level of theory and the experimental values. For gold, the CCSD(T)-F12b values needed to be corrected for spin−orbit relativistic effects to obtain good agreement with experiment. Electronic properties including the HOMO−LUMO gaps for the even clusters and the spin densities for the odd clusters were calculated. The lowest gap is predicted to occur for n = 16 where the HOMO and LUMO are very similar in shape.

The catalyzed hydrogenation of CO2 to formate via a triphosphine-ligated Cu­(I) was studied computationally at the density functional theory level in the presence of a self-consistent reaction field. Of the four functionals benchmarked, M06 was generally in the best agreement with the available experimentally estimated values. Two bases, DBU and TBD, were studied in the context of two proposed mechanisms in the MeCN solvent. Activation of H2 was explored by using LCu­(DBU)+ to form LCuH. Dissociation of a ligand arm results in higher barriers to form the key hydride complex, LCuH. The preferred mechanism passes through a transition state, where the H2 has one H atom interacting with the copper center and the other H atom interacting with the N atom of the base, similar to H2 insertion into a frustrated Lewis pair. There is no significant difference between the choice of a base, DBU or TBD, with respect to the proposed mechanisms. We propose that the experimentally observed differences between DBU and TBD reactivities for this mechanism are due to off-pathway changes.

The chemisorption addition of CO 2 to M 3 O 6 and M 3 O 6− for M = Ti, Zr, and Hf was examined using couple cluster CCSD(T) theory using density functional theory B3LYP geometries. For neutral M 3 O 6 CO 2 , a bridge chemisorbed tridentate carbonate cluster is the lowest energy for Ti and Zr, and a terminal chemisorbed bidentate carbonate is the lowest energy for Hf. For anionic M 3 O 6 CO 2 − , the lowest energy structure is a terminal chemisorbed bidentate carbonate for all three metals. The use of correlation-consistent weighted core basis sets for the CCSD(T) calculations is shown to be necessary to obtain the correct energy ordering for the isomers. Only for Ti 3 O 6 CO 2 − is a center tridentate carbonate cluster a low energy isomer. The electron affinities of M 3 O 6 CO 2 are ∼0.2 eV larger than for M 3 O 6 . The CO 2 chemisorption binding energies increase slightly for M 3 O 6 − as compared to those for M 3 O 6 .

In catalysis, MgO is often used to modify the acid–base properties of support oxides and to stabilize supported metal atoms and particles on oxides. In this study, we show how the sublimation of MgO powder can be used to deposit MgO monomers, hither on anatase TiO2(101). A combination of x-ray electron spectroscopy, high-resolution scanning tunneling microscopy, and density functional theory is employed to gain insight into the MgO monomer binding, electronic and vibrational properties, and thermal stability. In the most stable configuration, the Mg and O of the MgO monomer bind to two surface oxygens and one undercoordinated surface titanium, respectively. The additional binding weakens the Mg–O monomer bond and makes Mg more ionic. The monomers are thermally stable up to 600 K, where the onset of diffusion into the TiO2 bulk is observed. The monomeric MgO species on TiO2(101) represent an ideal atomically precise system with modified acid–base properties and will be employed in our future catalytic studies.

Addition of trivalent chromium, Cr­(III), to solutions undergoing electrospray ionization (ESI) enhances protonation and leads to formation of [M + 2H]2+ for peptides that normally produce [M + H]+. This effect is explored using electronic structure calculations at the density functional theory (DFT) level to predict the energetics of various species that are potentially important to the mechanism. Gas- and solution-phase reaction free energies for glycine and its anion reacting with [Cr­(III)­(H2O)6]3+ and for dehydration of these species have been predicted, where glycine is used as a simple model for a peptide. For comparison, calculations were also performed with Fe­(III), Al­(III), Sc­(III), Y­(III), and La­(III). Removal of water from these complexes, as would occur during the ESI desolvation process, results in species that are highly acidic. The calculated pK a of Cr­(III) with a single solvation shell is −10.8, making [Cr­(III)­(H2O)6]3+ a superacid that is more acidic than sulfuric acid (pK a = −8.8). Binding to glycine requires removal of two aqua ligands, which gives [Cr­(III)­(H2O)4]3+ that has an extremely acidic pK a of −28.8. Removal of additional water further enhances acidity, reaching a pK a of −84.7 for [Cr­(III)­(H2O)]3+. A mechanism for enhanced protonation is proposed that incorporates computational and experiment results, as well as information on the known chemistry of Cr­(III), which is substitutionally inert. The initial step involves binding of [Cr­(III)­(H2O)4]3+ to the deprotonated C-terminus of a peptide. As the drying process during ESI strips water from the complex, the resulting superacid transfers protons to the bound peptide, eventually leading to formation of [M + 2H]2+.