Infrared Multiple Photon Dissociation Spectroscopy of Hydrated Cobalt Anions Doped with Carbon Dioxide CoCO2 (H2 O)n - , n=1-10, in the C-O Stretch Region.

We investigate anionic [Co,CO2 ,nH2 O]- clusters as model systems for the electrochemical activation of CO2 by infrared multiple photon dissociation (IRMPD) spectroscopy in the range of 1250-2234 cm-1 using an FT-ICR mass spectrometer. We show that both CO2 and H2 O are activated in a significant fraction of the [Co,CO2 ,H2 O]- clusters since it dissociates by CO loss, and the IR spectrum exhibits the characteristic C-O stretching frequency. About 25 % of the ion population can be dissociated by pumping the C-O stretching mode. With the help of quantum chemical calculations, we assign the structure of this ion as Co(CO)(OH)2 - . However, calculations find Co(HCOO)(OH)- as the global minimum, which is stable against IRMPD under the conditions of our experiment. Weak features around 1590-1730 cm-1 are most likely due to higher lying isomers of the composition Co(HOCO)(OH)- . Upon additional hydration, all species [Co,CO2 ,nH2 O]- , n≥2, undergo IRMPD through loss of H2 O molecules as a relatively weakly bound messenger. The main spectral features are the C-O stretching mode of the CO ligand around 1900 cm-1 , the water bending mode mixed with the antisymmetric C-O stretching mode of the HCOO- ligand around 1580-1730 cm-1 , and the symmetric C-O stretching mode of the HCOO- ligand around 1300 cm-1 . A weak feature above 2000 cm-1 is assigned to water combination bands. The spectral assignment clearly indicates the presence of at least two distinct isomers for n ≥2.

Probing the Structural Evolution of the Hydrated Electron in Water Cluster Anions (H2O)n-, n ≤ 200, by Electronic Absorption Spectroscopy.

Electronic absorption spectra of water cluster anions (H2O)n-, n ≤ 200, at T = 80 K are obtained by photodissociation spectroscopy and compared with simulations from literature and experimental data for bulk hydrated electrons. Two almost isoenergetic electron binding motifs are seen for cluster sizes 20 ≤ n ≤ 40, which are assigned to surface and partially embedded isomers. With increasing cluster size, the surface isomer becomes less populated, and for n ≥ 50, the partially embedded isomer prevails. The absorption shifts to the blue, reaching a plateau at n ≈ 100. In this size range, the absorption spectrum is similar to that of the bulk hydrated electron but is slightly red-shifted; spectral moment analysis indicates that these clusters are reasonable model systems for hydrated electrons near the liquid-vacuum interface.

Infrared Spectroscopy of Size-Selected Hydrated Carbon Dioxide Radical Anions CO2 .- (H2 O)n (n=2-61) in the C-O Stretch Region.

Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO2 .- (H2 O)n is relevant for electrochemical carbon dioxide functionalization. CO2 .- (H2 O)n (n=2-61) is investigated by using infrared action spectroscopy in the 1150-2220 cm-1 region in an ICR (ion cyclotron resonance) cell cooled to T=80 K. The spectra show an absorption band around 1280 cm-1 , which is assigned to the symmetric C-O stretching vibration νs . It blueshifts with increasing cluster size, reaching the bulk value, within the experimental linewidth, for n=20. The antisymmetric C-O vibration νas is strongly coupled with the water bending mode ν2 , causing a broad feature at approximately 1650 cm-1 . For larger clusters, an additional broad and weak band appears above 1900 cm-1 similar to bulk water, which is assigned to a combination band of water bending and libration modes. Quantum chemical calculations provide insight into the interaction of CO2 .- with the hydrogen-bonding network.

Carbon-carbon bond formation in the reaction of hydrated carbon dioxide radical anions with 3-butyn-1-ol.

Electrochemical activation of carbon dioxide in aqueous solution is a promising way to use carbon dioxide as a C1 building block. Mechanistic studies in the gas phase play an important role to understand the inherent chemical reactivity of the carbon dioxide radical anion. Here, the reactivity of CO2 •-(H2O)n with 3-butyn-1-ol is investigated by Fourier transform ion cyclotron (FT-ICR) mass spectrometry and quantum chemical calculations. Carbon-carbon bond formation takes places, but is associated with a barrier. Therefore, bond formation may require uptake of several butynol molecules. The water molecules slowly evaporate from the cluster due to the absorption of room temperature black-body radiation. When all water molecules are lost, butynol evaporation sets in. In this late stage of the reaction, side reactions occur including H• atom transfer and elimination of HOCO•.

Photochemistry of glyoxylate embedded in sodium chloride clusters, a laboratory model for tropospheric sea-salt aerosols.

Although marine aerosols undergo extensive photochemical processing in the troposphere, a molecular level understanding of the elementary steps involved in these complex reaction sequences is still missing. As a defined laboratory model system, the photodissociation of sea salt clusters doped with glyoxylate, [NanCln-2(C2HO3)]+, n = 5-11, is studied by a combination of mass spectrometry, laser spectroscopy and ab initio calculations. Glyoxylate acts as a chromophore, absorbing light below 400 nm via two absorption bands centered at about 346 and 231 nm. Cluster fragmentation dominates, which corresponds to internal conversion of the excited state energy into vibrational modes of the electronic ground state and subsequent unimolecular dissociation. Photochemical dissociation pathways in electronically excited states include CO and HCO elimination, leading to [Nan-xCln-x-2HCOO]+ and [NanCln-2COO˙]+ with typical quantum yields in the range of 1-3% and 5-10%, respectively, for n = 5. The latter species contains CO2˙- stabilized by the salt environment. The comparison of different cluster sizes shows that the fragments containing a carbon dioxide radical anion appear in a broad spectral region of 310-380 nm. This suggests that the elusive CO2˙- species may be formed by natural processes in the troposphere. Based on the photochemical cross sections obtained here, the photolysis lifetime of glyoxylate in a dry marine aerosol is estimated as 10 h. Quantum chemical calculations show that dissociation along the C-C bond in glyoxylic acid as well as glyoxylate embedded in the salt cluster occurs after reaching the S1/S0 conical intersection, while this conical intersection is absent in free glyoxylate ions.

Infrared spectroscopy of O˙- and OH- in water clusters: evidence for fast interconversion between O˙- and OH˙OH.

We present infrared multiple photon dissociation (IRMPD) spectra of (H2O)nO˙- and (H2O)nOH- cluster ensembles for n[combining macron] ≈ 8 and 47 in the range of 2400-4000 cm-1. Both hydrated ions exhibit the same spectral features, in good agreement with theoretical calculations. Decomposition of the calculated spectra shows that bands originating from H2OO˙- and H2OOH- interactions span almost the whole spectral region of interest. Experimentally, evaporation of OH˙ is observed to a small extent, which requires interconversion of (H2O)nO˙- into (H2O)n-1OH˙OH-, with subsequent H2O evaporation preferred over OH˙ evaporation. The modeling shows that (H2O)nO˙- and (H2O)n-1OH˙OH- cannot be distinguished by IRMPD spectroscopy.

Photodissociation spectroscopy of protonated leucine enkephalin.

Protonated leucine enkephalin (YGGFL) was studied by ultraviolet photodissociation (UVPD) from 225 to 300 nm utilizing an optical parametric oscillator tunable wavelength laser system (OPO). Fragments were identified by absolute mass measurement in a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Bond cleavage was preferred in the vicinity of the two aromatic residues, resulting in high ion abundances for a4, a1, b3, y2 and y1 fragments. a, b and y ions dominated the mass spectrum, and full sequence coverage was achieved for those types. Photodissociation was most effective at the short wavelength end of the studied range, which is assigned to the onset of the La π-π* transition of the tyrosine chromophore, but worked well also at the Lb π-π* chromophore absorption maxima in the 35 000-39 000 cm-1 region. Several side-chain and internal fragments were observed. H atom loss is observed only above 41 000 cm-1, consistent with the requirement of a curve crossing to a repulsive 1πσ* state. It is suggested that the photochemically generated mobile H atom plays a role in further backbone cleavages, similar to the mechanism for electron capture dissociation. The b4 fragment is most intense at the Lb chromophore absorptions, undergoing additional fragmentation at higher photon energies. The high resolution of the FT-ICR MS revealed that out of all x and z-type fragments only x3 and x4 were formed, with low intensity. Other previously reported x- and z-fragments were re-assigned to internal fragments, based on exact mass measurement.