Diffuse Vibrational Signature of a Single Proton Embedded in the Oxalate Scaffold, HO2CCO2(-).

To understand how the D2d oxalate scaffold (C2O4)(2-) distorts upon capture of a proton, we report the vibrational spectra of the cryogenically cooled HO2CCO2(-) anion and its deuterated isotopologue DO2CCO2(-). The transitions associated with the skeletal vibrations and OH bending modes are sharp and are well described by inclusion of cubic terms in the normal mode expansion of the potential surface through an extended Fermi resonance analysis. The ground state structure features a five-membered ring with an asymmetric intramolecular proton bond. The spectral signatures of the hydrogen stretches, on the contrary, are surprisingly diffuse, and this behavior is not anticipated by the extended Fermi scheme. We trace the diffuse bands to very strong couplings between the high-frequency OH-stretch and the low-frequency COH bends as well as heavy particle skeletal deformations. A simple vibrationally adiabatic model recovers this breadth of oscillator strength as a 0 K analogue of the motional broadening commonly used to explain the diffuse spectra of H-bonded systems at elevated temperatures, but where these displacements arise from the configurations present at the vibrational zero-point level.

Mid-infrared signatures of hydroxyl containing water clusters: Infrared laser Stark spectroscopy of OH-H2O and OH(D2O)n (n = 1-3).

Small water clusters containing a single hydroxyl radical are synthesized in liquid helium droplets. The OH-H2O and OH(D2O)n clusters (n = 1-3) are probed with infrared laser spectroscopy in the vicinity of the hydroxyl radical OH stretch vibration. Experimental band origins are qualitatively consistent with ab initio calculations of the global minimum structures; however, frequency shifts from isolated OH are significantly over-predicted by both B3LYP and MP2 methods. An effective Hamiltonian that accounts for partial quenching of electronic angular momentum is used to analyze Stark spectra of the OH-H2O and OH-D2O binary complexes, revealing a 3.70(5) D permanent electric dipole moment. Computations of the dipole moment are in good agreement with experiment when large-amplitude vibrational averaging is taken into account. Polarization spectroscopy is employed to characterize two vibrational bands assigned to OH(D2O)2, revealing two nearly isoenergetic cyclic isomers that differ in the orientation of the non-hydrogen-bonded deuterium atoms relative to the plane of the three oxygen atoms. The dipole moments for these clusters are determined to be approximately 2.5 and 1.8 D for "up-up" and "up-down" structures, respectively. Hydroxyl stretching bands of larger clusters containing three or more D2O molecules are observed shifted approximately 300 cm(-1) to the red of the isolated OH radical. Pressure dependence studies and ab initio calculations imply the presence of multiple cyclic isomers of OH(D2O)3.

Infrared Spectroscopy of OH··CH3OH: Hydrogen-Bonded Intermediate Along the Hydrogen Abstraction Reaction Path.

Substantial non-Arrhenius behavior has been previously observed in the low temperature reaction between the hydroxyl radical and methanol. This behavior can be rationalized assuming the stabilization of an association adduct in the entrance channel of the reaction, from which barrier penetration via quantum mechanical tunneling produces the CH3O radical and H2O. Helium nanodroplet isolation and a serial pick-up technique are used to stabilize the hydrogen bonded prereactive OH··CH3OH complex. Mass spectrometry and infrared spectroscopy are used to confirm its production and probe the OH stretch vibrations. Stark spectroscopy reveals the magnitude of the permanent electric dipole moment, which is compared to ab initio calculations that account for wide-amplitude motion in the complex. The vibrationally averaged structure has Cs symmetry with the OH moiety hydrogen bonded to the hydroxyl group of methanol. Nevertheless, the zero-point level of the complex exhibits a wave function significantly delocalized over a bending coordinate leading to the transition state of the CH3O producing reaction.

Liquid hot NAGMA cooled to 0.4 K: benchmark thermochemistry of a gas-phase peptide.

Vibrational spectroscopy and helium nanodroplet isolation are used to determine the gas-phase thermochemistry for isomerization between conformations of the model dipeptide, N-acetylglycine methylamide (NAGMA). A two-stage oven source is implemented to produce a gas-phase equilibrium distribution of NAGMA conformers, which is preserved when individual molecules are captured and cooled to 0.4 K by He nanodroplets. With polarization spectroscopy, the IR spectrum in the NH stretch region is assigned to a mixture of two conformers having intramolecular hydrogen bonds composed of either five- or seven-membered rings, C5 and C7, respectively. The C5 to C7 interconversion enthalpy and entropy, obtained from a van't Hoff analysis, are -4.52 ± 0.12 kJ/mol and -12.4 ± 0.2 J/(mol · K), respectively. The experimental thermochemistry is compared to high-level electronic structure theory computations.

Microhydration of contact ion pairs in M(2+)OH(-)(H2O)(n=1-5) (M = Mg, Ca) clusters: spectral manifestations of a mobile proton defect in the first hydration shell.

Vibrational predissociation spectra of D2-"tagged" Mg(2+)OH(-)(H2O)n=1-6 and Ca(2+)OH(-)(H2O)n=1-5 clusters are reported to explore how the M(2+)OH(-) contact ion pairs respond to stepwise formation of the first hydration shell. In both cases, the hydroxide stretching frequency is found to red-shift strongly starting with addition of the third water molecule, quickly becoming indistinguishable from nonbonded OH groups associated with solvent water molecules by n = 5. A remarkably broad feature centered around 3200 cm(-1) and spanning up to ∼1000 cm(-1) appears for the n ≥ 4 clusters that we assign to a single-donor ionic hydrogen bond between a proximal first solvent shell water molecule and the embedded hydroxide ion. The extreme broadening is rationalized with a theoretical model that evaluates the range of local OH stretching frequencies predicted for the heavy particle configurations available in the zero-point vibrational wave function describing the low-frequency modes. The implication of this treatment is that extreme broadening in the vibrational spectrum need not arise from thermal fluctuations in the ion ensemble, but can rather reflect combination bands based on the OH stretching fundamental that involve many quanta of low-frequency modes whose displacements strongly modulate the OH stretching frequency.

Communication: Helium nanodroplet isolation and rovibrational spectroscopy of hydroxymethylene.

Hydroxymethylene (HCOH) and its d1-isotopologue (HCOD) are isolated in low temperature helium nanodroplets following pyrolysis of glyoxylic acid. Transitions identified in the infrared spectrum are assigned exclusively to the trans-conformation based on previously reported anharmonic frequency computations [P. R. Schreiner, H. P. Reisenauer, F. C. Pickard, A. C. Simmonett, W. D. Allen, E. Mátyus, and A. G. Császár, Nature 453, 906 (2008); L. Koziol, Y. M. Wang, B. J. Braams, J. M. Bowman, and A. I. Krylov, J. Chem. Phys. 128, 204310 (2008)]. For the OH(D) and CH stretches, a- and b-type transitions are observed, and when taken in conjunction with CCSD(T)/cc-pVTZ computations, lower limits to the vibrational band origins are determined. The relative intensities of the a- and b-type transitions provide the orientation of the transition dipole moment in the inertial frame. The He nanodroplet data are in excellent agreement with anharmonic frequency computations reported here and elsewhere, confirming an appreciable Ar-matrix shift of the OH and OD stretches and strong anharmonic resonance interactions in the high-frequency stretch regions of the mid-infrared.

Cryogenic ion chemistry and spectroscopy.

The use of mass spectrometry in macromolecular analysis is an incredibly important technique and has allowed efficient identification of secondary and tertiary protein structures. Over 20 years ago, Chemistry Nobelist John Fenn and co-workers revolutionized mass spectrometry by developing ways to non-destructively extract large molecules directly from solution into the gas phase. This advance, in turn, enabled rapid sequencing of biopolymers through tandem mass spectrometry at the heart of the burgeoning field of proteomics. In this Account, we discuss how cryogenic cooling, mass selection, and reactive processing together provide a powerful way to characterize ion structures as well as rationally synthesize labile reaction intermediates. This is accomplished by first cooling the ions close to 10 K and condensing onto them weakly bound, chemically inert small molecules or rare gas atoms. This assembly can then be used as a medium in which to quench reactive encounters by rapid evaporation of the adducts, as well as provide a universal means for acquiring highly resolved vibrational action spectra of the embedded species by photoinduced mass loss. Moreover, the spectroscopic measurements can be obtained with readily available, broadly tunable pulsed infrared lasers because absorption of a single photon is sufficient to induce evaporation. We discuss the implementation of these methods with a new type of hybrid photofragmentation mass spectrometer involving two stages of mass selection with two laser excitation regions interfaced to the cryogenic ion source. We illustrate several capabilities of the cryogenic ion spectrometer by presenting recent applications to peptides, a biomimetic catalyst, a large antibiotic molecule (vancomycin), and reaction intermediates pertinent to the chemistry of the ionosphere. First, we demonstrate how site-specific isotopic substitution can be used to identify bands due to local functional groups in a protonated tripeptide designed to stereoselectively catalyze bromination of biaryl substrates. This procedure directly reveals the particular H-bond donor and acceptor groups that enforce the folded structure of the bare ion as well as provide contact points for noncovalent interaction with substrates. We then show how photochemical hole-burning involving only vibrational excitations can be used in a double-resonance mode to systematically disentangle overlapping spectra that arise when several conformers of a dipeptide are prepared in the ion source. Finally, we highlight our ability to systematically capture reaction intermediates and spectroscopically characterize their structures. Through this method, we can identify the pathway for water-network-mediated, proton-coupled transformation of nitrosonium, NO(+) to HONO, a key reaction controlling the cations present in the ionosphere. Through this work, we reveal the critical role played by water molecules occupying the second solvation shell around the ion, where they stabilize the emergent product ion in a fashion reminiscent of the solvent coordinate responsible for the barrier to charge transfer in solution. Looking to the future, we predict that the capture and characterization of fleeting intermediate complexes in the homogeneous catalytic activation of small molecules like water, alkanes, and CO2 is a likely avenue rich with opportunity.

Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals.

Infrared spectra in the C-H stretch region are reported for the allyl (CH2CHCH2) and allyl peroxy (CH2=CH-CH2OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν1 (a1), ν3 (a1), and ν13 (b2) C-H stretch bands and four others to the ν14/(ν15+2ν11) (b2) and ν2/(ν4+2ν11) (a1) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν1 band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O2 following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC-OO and CC-CO bonds reveals multiple isomerization barriers greater than ≈300 cm(-1). Nevertheless, the C-H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O2 reaction within helium droplets.

Helium nanodroplet isolation and infrared spectroscopy of the isolated ion-pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

The ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was vaporized at 420 K, and the ion-pair constituents were entrained in a beam of liquid He nanodroplets and cooled to 0.4 K. The vapor pressure was optimized such that each He droplet picked up a single ion-pair from the gas phase. Infrared spectroscopy in the CH stretch region reveals bands that are assigned to intact ion-pairs on the basis of comparisons to ab initio harmonic frequency computations of 23 low energy isomers. The He droplet spectrum is consistent with a weighted sum of the computed harmonic spectra, in which the weights are determined from ab initio computations of the relative free energies at 420 K. Anharmonic resonance polyads in the CH stretch region are treated explicitly, which improves the agreement between the experiment and computed spectra for ion-pairs. For isomers having a strong cation···anion hydrogen bonding interaction, the imidazolium C(2)-H stretch fundamental is shifted to lower energy and into resonance with the overtones and combination bands of the imidazolium ring stretching modes, resulting in a spectral complexity in the CH stretch region that is fully resolved in the He droplet spectrum. The assignment of the infrared spectrum to ion-pairs is confirmed through polarization spectroscopy measurements that reveal the permanent electric dipole moment of the He-solvated species to be 11 ± 2 D. The computed permanent electric dipole moments for the low energy isomers of the [emim(+)][Tf2N(-)] ion-pairs fall in the range 9-13 D, whereas the computed dipole moments of decomposition products of the ionic liquid are less than 4.3 D.

Structural characterization of electron-induced proton transfer in the formic acid dimer anion, (HCOOH)2-, with vibrational and photoelectron spectroscopies.

The (HCOOH)(2) anion, formed by electron attachment to the formic acid dimer (FA(2)), is an archetypal system for exploring the mechanics of the electron-induced proton transfer motif that is purported to occur when neutral nucleic acid base-pairs accommodate an excess electron [K. Aflatooni, G. A. Gallup, and P. D. Burrow, J. Phys. Chem. A 102, 6205 (1998); J. H. Hendricks, S. A. Lyapustina, H. L. de Clercq, J. T. Snodgrass, and K. H. Bowen, J. Chem Phys. 104, 7788 (1996); C. Desfrancois, H. Abdoul-Carime, and J. P. Schermann, ibid. 104, 7792 (1996)]. The FA(2) anion and several of its H∕D isotopologues were isolated in the gas phase and characterized using Ar-tagged vibrational predissociation and electron autodetachment spectroscopies. The photoelectron spectrum of the FA(2) anion was also recorded using velocity-map imaging. The resulting spectroscopic information verifies the equilibrium FA(2)(-) geometry predicted by theory which features a symmetrical, double H-bonded bridge effectively linking together constituents that most closely resemble the formate ion and a dihydroxymethyl radical. The spectroscopic signatures of this ion were analyzed with the aid of calculated anharmonic vibrational band patterns.

Vibrational manifestations of strong non-Condon effects in the H3O(+)·X3 (X = Ar, N2, CH4, H2O) complexes: a possible explanation for the intensity in the "association band" in the vibrational spectrum of water.

The harmonic approximation provides a powerful approach for interpreting vibrational spectra. In this treatment, the energy and intensity of the 3N- 6 normal modes are calculated using a quadratic expansion of the potential energy and a linear expansion of the dipole moment surfaces, respectively. In reality, transitions are often observed that are not accounted for by this approach (e.g. combination bands, overtones, etc.), and these transitions arise from inherent anharmonicities present in the system. One interesting example occurs in the vibrational spectrum of H(2)O((l)), where a band is observed near 2000 cm(-1) that is commonly referred to as the "association band". This band lies far from the expected bend and stretching modes of the water molecule, and is not recovered at the harmonic level. In a recent study, we identified a band in this spectral region in gas-phase clusters involving atomic and molecular adducts to the H(3)O(+) ion. In the current study we probe the origins of this band through a systematic analysis of the argon-predissociation spectra of H(3)O(+)·X(3) where X = Ar, CH(4), N(2) or H(2)O, with particular attention to the contributions from the non-linearities in the dipole surfaces, often referred to as non-Condon effects. The spectra of the H(3)O(+) clusters all display strong transitions between 1900-2100 cm(-1), and theoretical modeling indicates that they can be assigned to a combination band involving the HOH bend and frustrated rotation of H(3)O(+) in the solvent cage. This transition derives its oscillator strength entirely from strong non-Condon effects, and we discuss its possible relationship to the association band in the spectrum of liquid water.

Determination of noncovalent docking by infrared spectroscopy of cold gas-phase complexes.

Multidentate, noncovalent interactions between small molecules and biopolymer fragments are central to processes ranging from drug action to selective catalysis. We present a versatile and sensitive spectroscopic probe of functional groups engaged in hydrogen bonding in such contexts. This involves measurement of the frequency changes in specific covalent bonds upon complex formation, information drawn from otherwise transient complexes that have been extracted from solution and conformationally frozen near 10 kelvin in gas-phase clusters. Resonances closely associated with individual oscillators are easily identified through site-specific isotopic labeling, as demonstrated by application of the method to an archetypal system involving a synthetic tripeptide known to bind biaryl substrates through tailored hydrogen bonding to catalyze their asymmetric bromination. With such data, calculations readily converge on the plausible operative structures in otherwise computationally prohibitive, high-dimensionality landscapes.

Isomer-Specific IR-IR Double Resonance Spectroscopy of D2-Tagged Protonated Dipeptides Prepared in a Cryogenic Ion Trap.

Isomer-specific vibrational predissociation spectra are reported for the gas-phase GlySarH(+) and SarSarH(+) [Gly = glycine; Sar = sarcosine] ions prepared by electrospray ionization and tagged with weakly bound D2 adducts using a cryogenic ion trap. The contributions of individual isomers to the overlapping vibrational band patterns are completely isolated using a pump-probe photochemical hole-burning scheme involving two tunable infrared lasers and two stages of mass selection (hence IR(2)MS(2)). These patterns are then assigned by comparison with harmonic (MP2/6-311+G(d,p)) spectra for various possible conformers. Both systems occur in two conformations based on cis and trans configurations with respect to the amide bond. In addition to the usual single intramolecular hydrogen bond motif between the protonated amine and the nearby amide oxygen atom, cis-SarSarH(+) adopts a previous unreported conformation in which both amino NH's act as H-bond donors. The correlated red shifts in the NH donor and C═O acceptor components of the NH···O═C linkage to the acid group are unambiguously assigned in the double H-bonded conformer.

NH+-F hydrogen bonding in a fluorinated "proton sponge" derivative: integration of solution, solid-state, gas-phase, and computational studies.

We report detailed studies on the characterization of an intramolecular NH-F hydrogen bond formed within a fluorinated "proton sponge" derivative. An ammonium ion, generated from 8-fluoro-N,N-dimethylnaphthalen-1-amine, serves as a charged hydrogen bond donor to a covalently bound fluorine appropriately positioned on the naphthalene skeleton. Potentiometric titrations of various N,N-dimethylnaphthalen-1-amines demonstrate a significant increase in basicity when hydrogen bonding is possible. X-ray crystallography reveals that NH-F hydrogen bonding in protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine is heavily influenced by ion pairing in the solid state; bifurcated and trifurcated hydrogen bonds are formed depending on the counterion utilized. Compelling evidence of hydrogen bonding in the 8-fluoro-N,N-dimethylnaphthyl-1-ammonium cation is provided by gas-phase cryogenic vibrational photodissociation spectroscopy. Solution-phase infrared spectroscopy provides complementary results, and the frequencies of the N-H stretching mode in both phases are in excellent agreement with the computed vibrational spectra. NMR analysis of protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine demonstrates significant H-F coupling between the N-H hydrogen and fluorine that cannot be attributed to long-range, through-bond interactions; the couplings correlate favorably with calculated values. The results obtained from these experiments are congruent with the formation of an NH-F hydrogen bond upon protonation of 8-fluoro-N,N-dimethylnaphthalen-1-amine.

Characterizing the intramolecular H-bond and secondary structure in methylated GlyGlyH+ with H2 predissociation spectroscopy.

We report vibrational predissociation spectra of the four protonated dipeptides derived from glycine and sarcosine, GlyGlyH(+)•(H(2))(1,2), GlySarH(+)•(D(2))(2), SarGlyH(+)•(H(2))(2), and SarSarH(+)•(D(2))(2), generated in a cryogenic ion trap. Sharp bands were recovered by monitoring photoevaporation of the weakly bound H(2) (D(2)) molecules in a linear action regime throughout the 700-4200 cm(-1) range using a table-top laser system. The spectral patterns were analyzed in the context of the low energy structures obtained from electronic structure calculations. These results indicate that all four species are protonated on the N-terminus, and feature an intramolecular H-bond involving the amino group. The large blue-shift in the H-bonded N-H fundamental upon incorporation of a methyl group at the N-terminus indicates that this modification significantly lowers the strength of the intramolecular H-bond. Methylation at the amide nitrogen, on the other hand, induces a significant rotation (~110°) about the peptide backbone.

Vibrational characterization of simple peptides using cryogenic infrared photodissociation of H2-tagged, mass-selected ions.

We present infrared photodissociation spectra of two protonated peptides that are cooled in a ~10 K quadrupole ion trap and "tagged" with weakly bound H(2) molecules. Spectra are recorded over the range of 600-4300 cm(-1) using a table-top laser source, and are shown to result from one-photon absorption events. This arrangement is demonstrated to recover sharp (Δν ~6 cm(-1)) transitions throughout the fingerprint region, despite the very high density of vibrational states in this energy range. The fundamentals associated with all of the signature N-H and C=O stretching bands are completely resolved. To address the site-specificity of the C=O stretches near 1800 cm(-1), we incorporated one (13)C into the tripeptide. The labeling affects only one line in the complex spectrum, indicating that each C=O oscillator contributes a single distinct band, effectively "reporting" its local chemical environment. For both peptides, analysis of the resulting band patterns indicates that only one isomeric form is generated upon cooling the ions initially at room temperature into the H(2) tagging regime.

Infrared multiple photon dissociation spectroscopy of sodium and potassium chlorate anions.

The structures of gas-phase, metal chlorate anions with the formula [M(ClO(3))(2)](-), M = Na and K, were determined using tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy. Structural assignments for both anions are based on comparisons of the experimental vibrational spectra for the two species with those predicted by density functional theory (DFT) and involve conformations that feature either bidentate or tridentate coordination of the cation by chlorate. Our results strongly suggest that a structure in which both chlorate anions are bidentate ligands is preferred for [Na(ClO(3))(2)](-). However, for [K(ClO(3))(2)](-) the best agreement between experimental and theoretical spectra is obtained from a composite of predicted spectra for which the chlorate anions are either both bidentate or both tridentate ligands. In general, we find that the overall accuracy of DFT calculations for prediction of IR spectra is dependent on both functional and basis set, with best agreement achieved using frequencies generated at the B3LYP/6-311+g(3df) level of theory.

Spectroscopic evidence for mobilization of amide position protons during CID of model peptide ions.

Infrared multiple photon dissociation (IRMPD) spectroscopy was used to study formation of b2+ from nicotinyl-glycine-glycine-methyl ester (NicGGOMe). IRMPD shows that NicGGOMe is protonated at the pyridine ring of the nicotinyl group, and more importantly, that b2+ from NicGGOMe is not protonated at the oxazolone ring, as would be expected if the species were generated on the conventional bn+/yn+ oxazolone pathway, but at the pyridine ring instead. IRMPD data support a hypothesis that formation of b2+ from NicGGOMe involves mobilization and transfer of an amide position proton during the fragmentation reaction.

Infrared spectrum of potassium-cationized triethylphosphate generated using tandem mass spectrometry and infrared multiple photon dissociation.

Tandem mass spectrometry and wavelength-selective infrared photodissociation were used to generate an infrared spectrum of gas-phase triethylphosphate cationized by attachment of K(+). Prominent absorptions were observed in the region of 900 to 1300 cm(-1) that are characteristic of phosphate P=O and P-O-R stretches. The relative positions and intensities of the IR absorptions were reproduced well by density functional theory (DFT) calculations performed using the B3LYP functional and the 6-31+G(d), 6-311+G(d,p) and 6-311++G(3df,2pd) basis sets. Because of good correspondence between experiment and theory for the cation, DFT was then used to generate a theoretical spectrum for neutral triethylphosphate, which in turn accurately reproduces the IR spectrum of the neat liquid when solvent effects are included in the calculations.

Cerium oxyhydroxide clusters: formation, structure, and reactivity.

Cerium oxyhydroxide cluster anions were produced by irradiating ceric oxide particles by using 355 nm laser pulses that were synchronized with pulses of nitrogen gas admitted to the irradiation chamber. The gas pulse stabilized the nascent clusters that are largely anhydrous [Ce(x)O(y)] ions and neutrals. These initially formed species react with water, principally forming oxohydroxy species that are described by the general formula [Ce(x)O(y)(OH)(z)](-) for which all the Ce atoms are in the IV oxidation state. In general, the extent of hydroxylation varies from a value of three OH per Ce atom when x = 1 to a value slightly greater than 1 for x >or= 8. The Ce(3) and Ce(6) species deviate significantly from this trend: the x = 3 cluster accommodates more hydroxyl moieties compared to neighboring congeners at x = 2 and 4. Conversely, the x = 6 cluster is significantly less hydroxylated than its x = 5 and 7 neighbors. Density functional theory (DFT) modeling of the cluster structures shows that the hydrated clusters are hydrolyzed, and contain one-to-multiple hydroxide moieties, but not datively bound water. DFT also predicts an energetic preference for formation of highly symmetric structures as the size of the clusters increases. The calculated structures indicate that the ability of the Ce(3) oxyhydroxide to accommodate more extensive hydroxylation is due to a more open, hexagonal structure in which the Ce atoms can participate in multiple hydrolysis reactions. Conversely the Ce(6) oxyhydroxide has an octahedral structure that is not conducive to hydrolysis. In addition to the fully oxidized (Ce(IV)) oxyhydroxides, reduced oxyhydroxides (containing a Ce(III) center) are also formed. These become more prominent as the size of the clusters increases, suggesting that the larger ceria clusters have an increased ability to accommodate a reduced Ce(III) moiety. In addition, the spectra offer evidence for the formation of superoxide derivatives that may arise from reaction of the reduced oxyhydroxides with dioxygen. The overall intensity of the clusters tends to monotonically decrease as the cluster size increases; however, this trend is interrupted at Ce(13), which is significantly more stable compared to neighboring congeners, suggesting formation of a dehydrated Keggin-type structure.