Solvation of O(2)(-) and O(4)(-) by p-difluorobenzene and p-xylene studied by photoelectron spectroscopy.

Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes.

Reactions between CO and small molybdenum suboxide cluster anions.

Reaction products resulting from small molybdenum suboxide cluster anions and carbon monoxide were studied with both mass spectrometry and anion photoelectron (PE) spectroscopy. In addition to the C6O6- product proposed previously, a number of unsaturated carbonyls were identified as terminal products in these reactions. A new PE spectrum of what may be C6O6-, in which the contribution from the Fe(CO)4- contaminant is subtracted, is reported. Additionally, the PE spectra of Mo(CO)5-, MoO(CO)3-, and MoO2(CO)n- (n=1 and 2) are presented, along with a new PE spectrum of an additional contaminant, Ni(CO)3-. Evidence of photodissociation of MoO(CO)3- to MoO-+3 CO is observed in the PE spectrum of MoO(CO)3-.

Production of C6O6- from oligomerization of CO on molybdenum anions.

C6O6- has been observed in mass spectra of the anionic reaction products between small molybdenum suboxide clusters and carbon monoxide. No other free oxocarbanions were observed, nor were any dianions. The anion photoelectron spectrum of C6O6- shows that the neutral has an adiabatic electron affinity of 2.54(5) eV and an excited triplet state with a term energy of 1.0(1) eV. Analysis of the mass spectra suggests that C6O6- may be forming from oligomerization of CO on bare or highly reduced molybdenum anion centers.

Addition of NH3 to Al3O3-.

Recent computational studies on the addition of ammonia (NH3) to the Al3O3- cluster anion [A. Guevara-Garcia, A. Martinez, and J. V. Ortiz, J. Chem. Phys. 122, 214309 (2005)] have motivated experimental and additional computational studies, reported here. Al3O3- is observed to react with a single NH3 molecule to form the Al3O3NH3- ion in mass spectrometric studies. This is in contrast to similarly performed studies with water, in which the Al3O5H4- product was highly favored. However, the anion PE spectrum of the ammoniated species is very similar to that of Al3O4H2-. The adiabatic electron affinity of Al3O3NH3 is determined to be 2.35(5) eV. Based on comparison between the spectra and calculated electron affinities, it appears that NH3 adds dissociatively to Al3O3-, suggesting that the time for the Al3O3-NH3 complex to either overcome or tunnel through the barrier to proton transfer (which is higher for NH3 than for water) is short relative to the time for collisional cooling in the experiment.

Reactivity of small Mo(x)Oy- clusters toward methane and ethane.

The reactions of Mo2Oy- suboxide clusters with both methane and ethane have been studied with a combination of mass spectrometry, anion photoelectron spectroscopy, and density functional theory calculations. Reactions were carried out under "gentle" and "violent" conditions. For methane, a number of products appeared under the gentler source conditions that were more logically attributed to dissociation of Mo2Oy- clusters upon reacting with methane to form MoCH2-, Mo(O)CH2-, and HMo(O2)CH3-. With ethane, products observed under the same gentle conditions were Mo(O)C2H2-, Mo(O)C2H4-, Mo(O2)C2H4-, and Mo(O2)(C2H5)2-. As expected, more products were observed when the reactions were carried out under violent conditions. The photoelectron spectra obtained for these species were compared to calculated adiabatic and vertical electron affinities and vibrational frequencies, leading to definitive structural assignments for several of the products.

Efficient low-temperature oxidation of carbon-cluster anions by SO2.

Carbon-cluster anions, CN-, are very reactive toward SO2 (sticking probability of 0.012 +/- 0.005 for C27- at 25 degrees C), in contrast to their inertness toward other common atmospheric gases and pollutants. In flow reactor experiments at ambient temperature and near atmospheric pressure, primary adsorption of SO2 by the carbon cluster anions, N = 4-60, yields CNSO2- or CN-1S-. The inferred elimination of neutral CO2 is also detected as meta-stable decay in collision-induced dissociation. At higher temperatures, the reaction of SO2 with nascent carbon clusters yields CN-1SO- as well as undetected CO. The size-dependent initial reactivity reflects the previously established structural transitions (i.e., from chain to cyclic to cage structures). Such carbon clusters are formed in sooting flames and may act as nuclei for the formation of primary soot particles and serve as models for the local structural features of active soot particle sites for black-carbon soot. The facile generation of reactive carbon-sulfide and -sulfinate units may therefore have implications for understanding the health and environmental effects attributed to the coincidence of soot and SO2.

Adsorption of carbon monoxide on smaller gold-cluster anions in an atmospheric-pressure flow-reactor: temperature and humidity dependence.

In the absence of moisture and at room temperature, the activity and saturation of CO on gold cluster anions, Au(N)-, are known to be highly dependent on the size of the cluster. Small Au(N)- clusters (N = 2,3) showed no adsorption activity, and the saturation CO adsorption values did not increase proportionately to cluster size or area. Here, we report on the effects of water vapor and temperature on the ability of Au(N)- clusters to adsorb CO in a high-pressure, fast-flow reactor. In contrast to all earlier reports, our results using this method show that smaller gold-cluster anions bind single and multiple CO groups at ambient temperature and above. In particular, species previously unseen at room temperature, corresponding to Au2(CO)-, Au3(CO) and Au4(CO)2, have been observed. Apparently, the presence of water vapor facilitates the adsorption of CO on the smaller clusters, possibly by aiding in the release of adsorption energy. As the number of studies concerning gold catalysis has continually increased over the past decade, these results provide important new information on the possible role of moisture in gold catalysis.

Oxygen adsorption on hydrated gold cluster anions: experiment and theory.

The discovery that supported gold clusters act as highly efficient catalysts for low-temperature oxidation reactions has led to a great deal of work aimed at understanding the origins of the catalytic activity. Several studies have shown that the presence of trace moisture is required for the catalysts to function. Using near-atmospheric pressure flow reactor techniques, we have studied humidity and temperature effects on the reactivity of gas-phase gold cluster anions with O2. Near room temperature, the humid source produces abundant gold-hydroxy cluster anions, Au(N)OH(-), and these have a reversed O2 adsorption activity: Nonreactive bare gold clusters become active when in the form Au(N)OH(-), while active bare clusters are inactive when -OH is bound. The binding energies for the stable structures obtained from density functional calculations confirm fully these findings. Moreover, the theory provides evidence that electron-transfer induced by the binding of a OH group enhances the reactivity toward molecular oxygen for odd anionic gold clusters and suppresses the reactivity for the even ones. The temperature dependence of O2 addition to Au(3)OH(-) and Au(4)(-) indicates deviations from equilibrium control at temperatures below room temperature. The effects of humidity on gold cluster adsorption activity support the conclusion drawn for the mechanism of O2 adsorption on "dry" gold cluster anions and provides insight into the possible role of water in the enhanced activity of supported gold cluster catalysts.