The adsorption of contaminants onto metal oxide surfaces with nanoscale Keggin-type structural topologies has been well established, but identification of the reactive sites and the exact binding mechanism are lacking. Polyaluminum species can be utilized as geochemical model compounds to provide molecular level details of the adsorption process. An Al30 Keggin-type species with two surface-bound Cu(2+) cations (Cu2Al30-S) has been crystallized in the presence of disulfonate anions and structurally characterized by single-crystal X-ray diffraction. Density functional theory (DFT) calculations of aqueous molecular analogues for Cu2Al30-S suggest that the reactivity of Al30 toward Cu(2+) and SO4(2-) shows opposite trends in preferred adsorption site as a function of particle topology, with anions preferring the beltway and cations preferring the caps. The bonding competition was modeled using two stepwise reaction schemes that consider Cu2Al30-S formation through initial Cu(2+) or SO4(2-) adsorption. The associated DFT energetics and charge density analyses suggest that strong electrostatic interactions between SO4(2-) and the beltway of Al30 play a vital role in governing where Cu(2+) binds. The calculated electrostatic potential of Al30 provides a theoretical interpretation of the topology-dependent reactivity that is consistent with the present study as well as other results in the literature.

Making use of a combination of ab initio calculated geometries, orbital energies, and orbital spatial distributions as well as experimental information about bond lengths, bond energies, vibrational frequencies, and dipole moments, the nature of the terminal PO bond in phosphates such as (MeO) 3 PO was probed and compared to the case in MeOsPdO where P is trivalent and a PO π bond is thus assumed to exist. We find that the MeOsP and terminal PO bond lengths in (MeO) 3 PO are essentially the same as in MeOsPdO and the terminal PO lengths are substantially shorter than single PsOMe bond lengths. We also find that the HOMO orbital energies in the two compounds are within 0.1 eV of one another and that these orbitals have spatial characteristics much like one would expect of a bonding π orbital connecting two atoms from different rows of the periodic table. Using this data, making a comparison to the more familiar bonding arising in N 2 , CO, and BF, and taking note of the dipole moments in compounds known to possess dative bonds, we conclude that it is best to represent the terminal PO bond in phosphates in terms of valence-bond structures such as (MeO) 3 PdO in which the formal charges are P 0 O 0 and where a single PO π bond exists. However, when it comes to characterizing the PO antibonding π* orbitals, significant differences arise. Electronic structure methods were able to identify the π* orbital of MeOsPdO and to determine its energy (the MeOsPdO -anion is even bound). Similar attempts to identify the PO π* orbital in the unbound (MeO) 3 PdO -anion lead us to conclude that this anion state is probably so strongly coupled to the continuum (i.e., to states corresponding to (MeO) 3 PdO plus a free electron) that it is so short lived as to be undetectable in experiments.

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Earlier work from this group has suggested that, in electron capture and electron-transfer mass spectrometry experiments on positively charged gas-phase samples of polypeptides, the initial electron attachment event most likely occurs at one of the peptide's positively charged sites (e.g., protonated side chains), although electron attachment can occur at a disulfide or amide site ca. 1-10% of the time. Focusing on the 90-99% dominant channel in which initial electron attachment occurs at a positive site, this paper addresses to what extent and over what distances electron transfer can take place from a positively charged site to a disulfide sigma* or amide pi* orbital, because it is thought that it is through such orbitals that disulfide or N-C(alpha) backbone bond cleavage occurs. Ab initio electronic structure calculations show that, as long as an SS sigma* (or OCN pi*) orbital experiences sufficient Coulomb stabilization from proximal positively charged groups, there are a myriad of excited Rydberg states located on positive sites that are able to induce such intrapeptide electron transfer. Computational data show that the transfer rates decay exponentially with distance for a given Rydberg orbital. An analytical model is developed that allows us to estimate the rates of Rydberg-to-valence and Rydberg-to-Rydberg electron transfers as functions of the Rydberg orbitals' n quantum numbers. This model suggests that transfer can occur over very long distances at rates that are more than competitive with the rates of radiationless relaxation within the manifold of Rydberg states (the latter processes eventually terminate the electron-transfer process an thus the disulfide or N-C(alpha) bond cleavages), and it gives formulas for how these rates depend on n (and thus the radial span of the Rydberg orbitals).

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