Photodissociation of noble metal-doped carbon clusters

Noble metal carbide cluster cations (MC(n)(+), M = Cu, Au) are produced by laser vaporization in a pulsed molecular beam and detected with time-of-flight mass spectrometry. Copper favors the formation of carbides with an odd number of carbon atoms, while gold shows marked drops in ion intensity after clusters with 3, 6, 9, and 12 carbons. These clusters are mass selected and photodissociated at 355 nm. Copper carbides with an odd number of carbons fragment by eliminating the metal from the cluster; for the small species it is eliminated as Cu(+) and for the larger species it is lost as neutral Cu. Copper carbides with an even number of carbons also lose the metal, but in addition to this they eliminate neutral C(3). This even-odd alternation, with the even clusters having mixed fragments, holds true for clusters as large as CuC(30)(+). No loss of C(2) is observed for even the largest clusters studied, indicating that fullerene formation does not occur. The gold carbide photodissociation data closely parallel that of copper, with even clusters losing primarily C(3) and odd ones losing gold. Comparisons to known carbon cluster ionization potentials give some insight into the structures of carbon photofragments. DFT calculations performed on CuC(3-11)(+) allow comparisons of the energetics of isomers likely present in our experiment, and metal-carbon dissociation energies help explain the even-odd alternation in the fragmentation channels. The simplest picture of these metal-doped carbides consistent with all the data is that the small species have linear chain structures with the metal attached at the end, whereas the larger species have cyclic structures with the metal attached externally to a single carbon.     

Photodissociation dynamics of IBr(-)(CO(2))(n), n<15

We report the ionic photoproducts produced following photoexcitation of mass selected IBr(-)(CO(2))(n), n=0-14, cluster ions at 790 and 355 nm. These wavelengths provide single state excitation to two dissociative states, corresponding to the A(') (2)Pi(1/2) and B 2 (2)Sigma(1/2) (+) states of the IBr(-) chromophore. Excitation of these states in IBr(-) leads to production of I(-)+Br and Br(-)+I( *), respectively. Potential energy curves for the six lowest electronic states of IBr(-) are calculated, together with structures for IBr(-)(CO(2))(n), n=1-14. Translational energy release measurements on photodissociated IBr(-) determine the I-Br(-) bond strength to be 1.10+/-0.04 eV; related measurements characterize the A(') (2)Pi(1/2)<--X (2)Sigma(1/2) (+) absorption band. Photodissociation product distributions are measured as a function of cluster size following excitation to the A(') (2)Pi(1/2) and B 2 (2)Sigma(1/2) (+) states. The solvent is shown to drive processes such as spin-orbit relaxation, charge transfer, recombination, and vibrational relaxation on the ground electronic state. Following excitation to the A(') (2)Pi(1/2) electronic state, IBr(-)(CO(2))(n) exhibits size-dependent cage fractions remarkably similar to those observed for I(2) (-)(CO(2))(n). In contrast, excitation to the B 2 (2)Sigma(1/2) (+) state shows extensive trapping in excited states that dominates the recombination behavior for all cluster sizes we investigated. Finally, a pump-probe experiment on IBr(-)(CO(2))(8) determines the time required for recombination on the ground state following excitation to the A(') state. While the photofragmentation experiments establish 100% recombination in the ground electronic state for this and larger IBr(-) cluster ions, the time required for recombination is found to be approximately 5 ns, some three orders of magnitude longer than observed for the analogous I(2) (-) cluster ion. Comparisons are made with similar experiments carried out on I(2) (-)(CO(2))(n) and ICl(-)(CO(2))(n) cluster ions.     

Saturated adsorption of CO and coadsorption of CO and O2 on AuN- (N=2-7) clusters

A first-principles quantum chemistry method, based on the Kohn-Sham density-functional theory, is used to investigate the adsorption of CO and O2 on small gas-phase gold cluster anions. The saturated adsorption of carbon monoxide on gold cluster anions AuN- (N=2-7) is discussed. The adsorption ability of CO reduces with the increase of the number of CO molecules bound to gold cluster anions, resulting in saturated adsorption at a certain amount of absorbed CO molecules, which is determined by geometric and electronic properties of gold clusters cooperatively. The effect of CO preadsorption on the electronic properties of gold cluster anions depends on the cluster size and the number of adsorbed CO, and the vertical detachment energies of CO-adsorbed gold cluster anions show a few changes with respect to corresponding pure gold cluster anions. The results indicate that the impinging adsorption of CO molecules may lead to geometry structure transformation on Au3- cluster. For the coadsorption of CO and O2 on Au2-, Au3- isomers, Au4-, and Au6-, we describe the cooperative adsorption between CO and O2, and find that the O2 dissociation is difficult on gas-phase gold cluster anions even with the preadsorption of CO.     

Cryogenic CO2 formation on oxidized gold clusters synthesized via reactive layer assisted deposition

Gas-phase Au atoms deposited onto a multilayer film of molecular oxygen produce atomic oxygen bound to gold clusters. After removal of molecular O2, temperature programmed desorption and molecular beam techniques show that the atomic oxygen readily reacts with CO to produce CO2. At present, the structure and size distribution of these clusters are unknown. Nevertheless, CO2 forms on these clusters upon exposure to CO at temperatures as low as 35 K. Furthermore, above 120 K, the reaction goes to completion with initial reaction yields as high as 50%.     

Solute-solvent interactions in microhydrate clusters: Carbazole - (H2O)n

We report the laser-induced fluorescence (LIF) and the resonant two-photon ionization spectra of the carbazole-(H₂O)_n (n = 1–3) hydrogen-bonded complexes. Use of carbazole as a symmetric “probe” molecule allows detailed insight into the symmetries, structures and intermolecular vibrations of these microhydrate complexes.     

A comparative ab initio study of Br2*- and Br2 water clusters

The work presents ab initio results on structure and electronic properties of Br2*-.nH2O(n=1-10) and Br2.nH2O(n=1-8) hydrated clusters to study the effects of an excess electron on the microhydration of the halide dimer. A nonlocal density functional, namely, Becke's half-and-half hybrid exchange-correlation functional is found to perform well on the present systems with a split valence 6-31++G(d,p) basis function. Geometry optimizations for all the clusters are carried out with several initial guess structures and without imposing any symmetry restriction. Br2*-.nH2O clusters prefer to have symmetrical double hydrogen-bonding structures. Results on Br2.nH2O(n>or=2) cluster show that the O atom of one H2O is oriented towards one Br atom and the H atom of another H2O is directed to other Br atom making Br2 to exist as Br+-Br- entity in the cluster. The binding and solvation energies are calculated for the Br2*-.nH2O and Br2.nH2O clusters. Calculations of the vibrational frequencies show that the formation of Br2*- and Br2 water clusters induces significant shifts from the normal modes of isolated water. Excited-state calculations are carried out on Br2*-.nH2O clusters following configuration interaction with single electron excitation procedure and UV-VIS absorption profiles are simulated. There is an excellent agreement between the present theoretical UV-VIS spectra of Br2*-.10H2O cluster and the reported transient optical spectra for Br2*- in aqueous solution.     

Photodissociation of metal-silicon clusters: encapsulated versus surface-bound metal

Metal-silicon cluster cations of the form MSi(n)+ (M = Cu, Ag, Cr) are produced in a molecular beam with pulsed laser vaporization. These species are mass-selected in a reflectron time-of-flight spectrometer and studied with laser photodissociation at 532 and 355 nm. For the noble metals copper and silver, photodissociation of the n = 7 and 10 clusters proceeds primarily by the loss of metal atoms, indicating that the metal is not located within the interior of silicon cages, and that metal-silicon bonding is weaker than silicon-silicon bonding. Chromium-silicon clusters for n = 7 also lose primarily the metal atom, but at n = 15 and 16 these dissociate via the loss of silicon, producing smaller metal-silicon species. This behavior is consistent with stronger metal-silicon bonding and encapsulated metal structures, as suggested previously by theory. MSi6(+) cations are produced efficiently in all of these photodissociation processes, indicating that these species have enhanced stability compared to other small clusters. Improved values are obtained for the ionization potentials of Si7 and Si10.     

Porous biomaterials obtained using supercritical CO 2- water emulsions

Highly porous, hydrophilic porous matrices were fabricated by using a high internal phase supercritical-CO2 (scCO2) emulsion templating technique. The novel aspect of the work resides in the combination of a natural biopolymer (dextran) as the building component of the matrices and of an environmentally benign solvent (supercritical-CO2) as the pore-generating phase. The synthetic route to the porous biomaterials involved the preliminary functionalization of the dextran chains with methacrylic moieties, formation of a scCO2-in-water concentrated emulsion, and curing of the external phase of the emulsion by radical polymerization. As the emulsion stabilizer a perfluoropolyether surfactant was chosen. The matrices obtained exhibit highly interconnected, trabecular morphologies. The porous biomaterial morphologies were qualitatively characterized by scanning electron microscopy (SEM) and the evaluation of void and interconnect sizes was carried out on the micrographs taken with the light microscope. To tailor the morphologies of the porous structures, the influence of the volume fraction of the internal phase and of the surfactant/internal phase ratio was investigated. It was established that the variation of the volume fraction of the internal phase exerted only a limited influence on void and interconnect sizes. On the contrary the increase of surfactant concentration alters dramatically the distribution of void size, a large proportion of the void space enclosed within the matrix being attributable to voids with a diameter exceeding 100 microm. The free toxic solvent process of fabrication of the porous structures, the high water content, the expected biocompatibility, and the mechanical properties that resemble natural tissues make these porous hydrogels potentially useful for tissue engineering applications.     

Amorphous solid water films: transport and guest-host interactions with CO2 and N2O dopants

Guest-host interactions have been examined experimentally for amorphous solid water (ASW) films doped with CO2 or N2O. The main diagnostics are Fourier transform infrared (FTIR) spectroscopy and temperature programmed desorption (TPD). ASW films deposited at 90 K are exposed to a dopant, and the first molecules that attach to a film enter its bulk until it is saturated with them. Subsequent dopant adsorption results in crystal growth atop the ASW film. There are distinct spectral signatures for these two cases: LO and TO vibrational modes for the crystal overlayer, and an easily distinguished peak for dopant molecules that reside within the ASW film. Above 105 K, the dopant surface layer desorbs fully. Some dopants residing within the ASW film remain until 155 K, at which point the ASW-to-crystalline-ice transition occurs, expelling essentially all of the dopant. No substantial differences are observed for CO2 versus N2O. It is shown that annealing an ASW film to 130 K lowers the film's capacity to include dopants by a factor of approximately 3, despite the fact that the ASW spectral feature centered at approximately 3250 cm(-1) shows no discernible change. Sandwiches were prepared: ASW-dopant-ASW etc., with the dopant layer displaying crystallinity. Raising these samples past 105 K resulted in the expulsion of essentially all of the crystalline dopant. What remained displayed the same spectral signature as the molecules that entered the bulk following adsorption at the surface. It is concluded that the adsorption sites, though prepared differently, have a lot in common. Dangling OH bonds were observed. When they interacted with a dopant, they underwent a red shift of approximately 50 cm(-1). This is in qualitative agreement with studies that have been carried out with weakly bound binary complexes. As a result of this study, a fairly complete, albeit qualitative, picture is in place for the adsorption, binding, and transport of CO2 and N2O in ASW films.     

Photodissociation of (SO2)m(H2O)n clusters employing femtosecond pump-probe spectroscopy

A femtosecond pump-probe technique was employed to study the photodissociation dynamics of (SO2)m(H2O)n clusters in real time for clusters, where m=1, 2 and n as large as 11. The pump (excitation) step occurs through a multiphoton process which populates the dissociative E state as well as a lower-lying bound state of the sulfur dioxide (SO2) chromophore. Dissociation of the SO2 monomer occurs through the E state and the decay is fit to a lifetime of 230 fs. The present study is in agreement with our previous investigations of homogeneous (SO2)m clusters that have shown that cluster formation inhibits the dissociation process owing to a steric effect induced by the cluster environment [K. L. Knappenberger, Jr. and A. W. Castleman, Jr., J. Chem. Phys. 121, 3540 (2004)]. The E state lifetime increases sequentially as a function of cluster size to as much as 668 fs when 11 water molecules solvate the chromophore. We have employed a method to compare the ratio of amplitude coefficients, which reflect a respective component of the mathematical fit, to determine the nature of the wave packet evolution in binary clusters. An increase of this ratio by as much as 440% was observed for large cluster sizes. A preferential ion state charge transfer, rather than dissociation, was observed in binary clusters. The significance of cluster size on evaporation processes has been investigated.     

Dielectric properties of water clusters containing CO and NO molecules. Computational experiment

The absorption of CO and NO molecules by (H₂O)₂₀ clusters was studied by the method of molecular dynamics. In general, the clusters containing CO molecules are more stable mechanically, while the clusters with NO molecules are more stable against heating. The mobility of NO molecules in such clusters is higher than that of CO molecules. The total dipole moment, the static dielectric permeability, the number of active electrons in the clusters, and the specific number of hydrogen bonds between water molecules possess peak values when the number of doping molecules i = 6. IR absorption spectra mostly acquire a smooth shape at i > 6. Capture of CO and NO molecules by water cluster operates as anti-greenhouse effect.     

DFT studies of Pt/Au bimetallic clusters and their interactions with the CO molecule

Density functional theory (DFT) calculations were performed to study Pt/Au clusters of different size, structure, and composition as well as their interactions with a CO molecule. Among the Pt/Au isomers studied here, the planar structure is the most stable structure in many Pt compositions, although three-dimensional structures become more stable with increasing Pt composition. Furthermore, structures with the Pt atoms surrounded by Au atoms are more stable among homotops. However, these conclusions will be altered if ligands are attached to the Pt/Au bimetallic clusters, as evidenced from the results of CO adsorption. When both Au and Pt sites are exposed, CO adsorption at the Pt site is stronger. If only a Au site is available for CO adsorption, the strongest adsorption occurs at approximately 25% Pt composition, which may correlate with the experimentally observed reactivity of the core-shell structured Pt/Au nanoparticles.     

Secondary bonding interactions in biomimetic [2Fe-2S] clusters

A series of synthetic [2Fe-2S] complexes with terminal thiophenolate ligands and tethered ether or thioether moieties has been prepared and investigated in order to provide models for the potential interaction of additional donor atoms with the Fe atoms in biological [2Fe-2S] clusters. X-ray crystal structures have been determined for six new complexes that feature appended Et (1(C)), OMe (1(O)), or SMe (1(S)) groups, or with a methylene group (2(C) ), an ether-O (2(O)), or an thioether-S (2(S)) linking two aryl groups. The latter two systems provide a constrained chelate arrangement that induces secondary bonding interactions with the ether-O and thioether-S, which is confirmed by density functional theory (DFT) calculations that also reveal significant spin density on those fifth donor atoms. Structural consequences of the secondary bonding interactions are analyzed in detail, and effects on the spectroscopic and electronic properties are probed by UV-vis, M?ssbauer, and (1)H NMR spectroscopy, as well by SQUID measurements and cyclic voltammetry. The potential relevance of the findings for biological [2Fe-2S] sites is considered.     

Influence of structure on electron correlation effects and electron-water dispersion interactions in anionic water clusters

Electronic structure calculations at the level of second-order M?ller-Plesset perturbation theory have been performed on anionic water clusters, (H2O)n(-), in the n = 14-33 size regime. The contribution to the electron binding energy that arises from electron correlation is found to be significantly larger for cavity-bound electrons than it is for surface-bound electrons, even for surface states with electron binding energies well above 1 eV. A decomposition of the correlation energy into interactions between pairs of Boys-localized molecular orbitals is used to demonstrate that the larger correlation energy found in the cavity isomers arises from electron-water dispersion interactions, and that the dispersion interaction is larger in cavity-bound isomers because the unpaired electron penetrates well beyond the first solvation shell. In contrast, a surface-bound electron exhibits virtually no penetration into the interior of the cavity. To obtain a qualitatively accurate picture of this phenomenon, one must plot molecular orbitals using isoprobability surfaces rather than arbitrarily-selected isocontours.     

Collisional energy transfer and fragmentation of size selected CO2 clusters

Carbon dioxide clusters are generated in a supersonic molecular beam and size selected by scattering from a He beam. By analyzing the measured time-of-flight spectra as a function of the deflection angle, differential energy loss spectra for (CO₂)₂ — He are obtained which show a rotational rainbow structure with a maximal energy transfer of ΔE/E=0.4. This result is compatible with the slipped parallel structure of dimer but not with theT-shaped geometry. The scattering analysis is also used to derive information about the pressure dependence of cluster formation and the fragmentation by electron impact ionisation. The latter process leads preferably to the monomer product ion CO ₂ ⁺ with a small but finite probability for other ionic channels.     

Photodissociation of room-temperature and jet-cooled water at 193 nm

The photodissociation dynamics of water in its first absorption band has been studied in detail by photolyzing room-tempera-ture and jet-cooled H₂O with an ArF excimer laser at 193 nm. The fate of the ejected OH(X ²Π) photofragments was probed by laser-induced fluorescence. The excess energy is transferred almost exclusively into translational motion of the products, ∂_t = 0.97. The rotational distribution depends strongly on the initial temperature. For warm water (T = 300 K), the rotational distribution can be described by a Boltzmann distribution with a temperature parameter of 400 K. No significant difference between the two Λ components, probed via Q and R, P lines, was observed. In the case of jet-cooled H₂O the rotational distribution of the Π⁻ component of the Λ doublets can be described by a temperature parameter of 330 K; that of the Π⁺ component strongly deviates from a Boltzmann distribution. The Λ doublet population shows an increasing inversion with increasing J_OH. The dissociation process does not distinguish between the two spin-orbit states and the spin is only a spectator in the dissociation process of H₂O at 193 nm. These results are compared with observations of the photolysis of water at 157 nm.     

Hydration process of Na2- in small water clusters: photoelectron spectroscopy and theoretical study of Na2- (H2O)n

Photoelectron spectroscopy (PES) of Na2- (H2O)n (n < or = 6) was investigated to examine the solvation of sodium aggregates in small water clusters. The PES bands for the transitions from the anion to the neutral ground and first excited states derived from Na2 (1(1)Sigmag+) and Na2 (1(3)Sigmau+) shifted gradually to the blue, and those to the higher-excited states correlated to the 3(2)S + 3(2)P asymptote dropped down rapidly to the red and almost degenerated on the 1(3)Sigmau+-type band at n = 4. Quantum chemical calculations for n up to 3 showed that the spectra can be ascribed to structures where one of the Na atoms is selectively hydrated. From the electron distributions, it is found that the Na- -Na+(H2O)n- -type electronic state grows with increasing cluster size, which can be regarded as a sign of the solvation of Na2- with ionization of the hydrated Na.     

Solution properties, electrochemical behavior and protein interactions of water soluble triosmium carbonyl clusters

The synthesis and solution chemistry of the water soluble clusters [Os₃(CO)₉(μ-η²-Bz)(μ-H)L⁺] (HBz=quinoxaline, L⁺=[P(OCH₂CH₂NMe₃)₃I₃], 1) along with its negatively charged analog [Os₃(CO)₉(μ-η²-Bz)(μ-H)L⁻] (L⁻=[P(C₆H₄SO₃)₃Na₃], 2) are reported. In addition, we have examined the reduction potentials of the complexes [Os₃(CO)₉(μ-η²-Bz)(μ-H)L] (HBz=phenanthridine, L=L⁺ (3); HBz=5,6 benzoquinoline, L=L⁺ (4); HBz=3-amino quinoline, L=L⁺ (5); HBz=3-amino quinoline, L=L⁻ (6). The neutral analog of 1 and 2 [Os₃(CO)₉(μ-η²-Bz)(μ-H) PPh₃] (Bz=quinoxaline, 7) was also examined for comparison. Both compounds 1 and 2 show pH dependent NMR spectra that are interpreted in terms of the extent of protonation of the uncoordinated quinoxaline nitrogen which impacts the degree of aggregation of the clusters in aqueous solution. Compound 1 undergoes a reversible 1e⁻ reduction in water while 2 undergoes a quasi-reversible 1e⁻ reduction at more negative potentials as expected from the difference in charge on the phosphine ligand. Compound 7 undergoes a marginally reversible CV in methylene chloride at a potential intermediate between the positively and negatively charged clusters. The overall stability of the radical anions of 1, 2 and 7 is somewhat less than the corresponding decacarbonyl [Os₃(CO)₁₀(μ-η²-Bz)(μ-H)] (HBz=quinoxaline). While complexes 1 and 2 show reversible 1e⁻ reductions, all the other complexes examined show 1e⁻ and/or two 1e⁻ irreversible reductions in aqueous and non-aqueous solvents. The potentials for these complexes follow expected trends relating to the charge on the phosphine and the pH of the aqueous solutions. The ligand dependent trends are compared with those of the previously reported corresponding decacarbonyls. The interactions of the positively and negatively charged clusters with albumin have been investigated using the transverse and longitudinal relaxation times of the hydride resonances as probes of binding to the protein. Evidence of binding is observed for both the positive and negative clusters but the positive and negative clusters exhibit distinctly different rotational correlation times. Two additional complexes [Os₃(CO)₉(μ-η²-Bz)(μ-H)L] (HBz=2-methylbenzimidazole, L=L⁺ (8); L=L⁻ (10) and HBz=quinoline-4-carboxaldehyde, L=L⁺ (9); L=L⁻ (11)) are reported in connection with these studies.