Electron bombardment induced fragmentation of size selected neutral (D2O) n clusters

The fragmentation behaviour of size selected neutral (D₂O) _n clusters withn4 after ionization with 70 eV electrons is subject of this work. Size selection by scattering the cluster beam from a He target beam in combination with a quadrupole mass filter and time resolved measurements at specific laboratory angles enables us to determine the neutral precursor masses of the detected ions. The measured fragment pattern is dominated by deuterated ions of the form (D₂O) _n–x D⁺ withx1. The dimer fragmentation which leads with a probability of 62.5% to the D₃O⁺ ion and with 37.5% to D₂O⁺ can be explained by fast intracluster ion-molecule reactions of charged monomer fragments reacting with the partner molecule. For larger clusters the fragmentation process can be rationalised by the creation of an initially highly excited D₃O⁺ (D₂O) _x complex which is stabilized by evaporating additional monomer units with the main fragment channel (D₂O)D⁺ forn=3 and (D₂O)₂D⁺ forn=4. With increasing cluster size an increasing tendency of evaporation of more than one water monomer unit has been observed.     

Magic numbers in sims of Mn similar to those of charged Ar clusters

Manganese cluster ions Mn _k ⁺ (k?60) have been produced by 7 keV Xe ion bombardment and analyzed by a double-focusing mass spectrometer. Discontinuous variations of intensity are found atk=5, 14, 16, 29, 34, 45 and 54. Most of these magic numbers coincide with or differ by only one from those observed in Ar _k ⁺ . The similarity in magic numbers between Mn _k ⁺ and Ar _k ⁺ indicates that the bonding nature in the charged Mn clusters is similar to that in the charged Ar clusters; The polarization force between a positive ion in the center of a cluster and surrounding neutral atoms is dominant binding force.     

MALDI-TOF Mass Spectrometry of Nanosized MoO<Subscript>2</Subscript>. Structure and Relative Stability of Isomers of Lower Molybdenum Oxide Cations

MALDI-TOF was used to study molybdenum dioxide (MoO₂) containing a nanosized fraction. The composition of cationic clusters of nonstoichiometric lower molybdenum oxides in the gas phase was determined, and the thermodynamic stabilities and configurations of isomers were calculated for selected symmetric molecular structures and for cations MoSO ₈ ⁺ and Mo₅O ₉ ⁺ . Molecular orbital analysis was performed for two trigonal-bipyramidal clusters Mo₅O₈ and Mo₅O₉. Changes in molybdenum–molybdenum interatomic distances in going from MoO ₈ ⁺ and Mo₅O ₉ ⁺ cations to neutral clusters are discussed.     

High Magnetic Moments in Manganese‐Doped Silicon Clusters

We report on the structural, electronic, and magnetic properties of manganese‐doped silicon clusters cations, Si_nMn⁺ with n=6–10, 12–14, and 16, using mass spectrometry and infrared spectroscopy in combination with density functional theory computations. This combined experimental and theoretical study allows several structures to be identified. All the exohedral Si_nMn⁺ (n=6–10) clusters are found to be substitutive derivatives of the bare Si_n+1⁺ cations, while the endohedral Si_nMn⁺ (n=12–14 and 16) clusters adopt fullerene‐like structures. The hybrid B3P86 functional is shown to be appropriate in predicting the ground electronic states of the clusters and in reproducing their infrared spectra. The clusters turn out to have high magnetic moments localized on Mn. In particular the Mn atoms in the exohedral Si_nMn⁺ (n=6–10) clusters have local magnetic moments of 4 μ_B or 6 μ_B and can be considered as magnetic copies of the silicon atoms. Opposed to other 3d transition‐metal dopants, the local magnetic moment of the Mn atom is not completely quenched when encapsulated in a silicon cage.     

Characterization of the fluxes of neutral and positively charged clusters (Agn and Agn+; n≤4) produced by argon ion sputtering of silver

The emission of neutral and positively charged silver clusters during sputtering of a polycrystalline silver target by 5 keV Ar⁺ ion bombardment has been studied and the sputter ejected silver flux has been characterized. As a result, the silver flux is found to be strongly dominated byneutral clusters rather than cluster ions. The contribution of neutral clusters in the overall silver flux decreases rapidly and monotonically with increasing cluster size n and decreases, in addition, with decreasing bombarding energy. The well known alternation of the secondary ion intensities of Ag _n ⁺ as a function of cluster size (higher intensities for odd n) is found to be correlated with the effective ionization potentials of the corresponding sputtered neutral clusters.     

[(TeMe2)Mn(CO)4(μ5-Te)(μ4-Te)Mn4(CO)12]−: A Pentacoordinate Bridging Tellurido Ligand in a Square-Pyramidal Geometry

The first Te–Mn–CO clusters were obtained by the thermal reaction of K₂TeO₃ with [Mn₂(CO)₁₀] in MeOH. The basicity of the μ₄-Te ligand in the octahedral cluster anion [(μ₄-Te)₂Mn₄(CO)₁₂]²⁻ is demonstrated by its binding to the fragment [(TeMe₂)Mn(CO)₄]⁺ in an axial fashion to afford the novel cluster 1 .     

On ionisation induced unimolecular dissociation of sodium clusters

Fragmentation of sodium cluster ions (Na _x ⁺ ,x<42) was studied via photoionisation of neutral precursors. Expansions of metal vapor out of cylindrical and conical nozzles yielded supersonic beams with differing cluster compositions. Measurements of photoionisation efficiency curves in the 3–6 eV range for both types of expansion allow quantitative separation of direct ionisation and unimolecular dissociation contributions to specific ion signals. Data for Na ₈ ⁺ and Na ₇ ⁺ are analysed to yield lower limits on bond energies. Results obtained for larger clusters are also discussed.     

Photoionization of Xe2, Xe3 and Xe4 in the 1024–1113 Å region

The mass spectra of Xe _n ⁺ clusters (n=2–13) were recorded using a supersonic beam and an ion time-of-flight mass analyser. The yield of Xe ₂ ⁺ , Xe ₃ ⁺ and Xe ₄ ⁺ cluster ions was measured with a resolution of 0.1 Å (1 meV) in the 1024–1113 Å (11.1–12.1 eV) region. Autoionizing Rydberg series of Xe₂ converging to theC ²_3/2u state of Xe ₂ ⁺ were observed in the spectrum of Xe ₂ ⁺ . The photoionization yield of Xe ₃ ⁺ and Xe ₄ ⁺ ions each displayed similar broad features that contained no fine structure corresponding to vibrational states. The broad features were assigned to autoionizing Rydberg series by analogy with the dimer ion spectrum.     

Structures,Unimolecular Fragmentations,and Reactivities of the Self‐Assembled Multimetallic/Peptide Complexes [Mnn(GlyGly‐H)2n−1]+ and [Mnn+1(GlyGly‐H)2n]2+

Complexes of Mn²⁺ with deprotonated GlyGly are investigated by sustained off‐resonance irradiation collision‐induced dissociation (SORI‐CID), infrared multiple‐photon dissociation spectroscopy, ion–molecule reactions, and computational methods. Singly [Mn_n(GlyGly‐H)_2n?1]⁺ and doubly [Mn_n+1(GlyGly‐H)_2n]²⁺ charged clusters are formed from aqueous solutions of MnCl₂ and GlyGly by electrospray ionization. The most intense ion produced was the singly charged [M₂(GlyGly‐H)₃]⁺ cluster. Singly charged clusters show extensive fragmentations of small neutral molecules such as water and carbon dioxide as well as dissociation pathways related to the loss of NH₂CHCO and GlyGly. For the doubly charged clusters, however, loss of GlyGly is observed as the main dissociation pathway. Structure elucidation of [Mn₃(GlyGly‐H)₄]²⁺ clusters has also been done by IRMPD spectroscopy as well as DFT calculations. It is shown that the lowest energy structure of the [Mn₃(GlyGly‐H)₄]²⁺ cluster is deprotonated at all carboxylic acid groups and metal ions are coordinated with carbonyl oxygen atoms, and that all amine nitrogen atoms are hydrogen bonded to the amide hydrogen. A comparison of the calculated high‐spin (sextet) and low‐spin (quartet) state structures of [Mn₃(GlyGly‐H)₄]²⁺ is provided. IRMPD spectroscopic results are in agreement with the lowest energy high‐spin structure computed. Also, the gas‐phase reactivity of these complexes towards neutral CO and water was investigated. The parent complexes did not add any water or CO, presumably due to saturation at the metal cation. However, once some of the ligand was removed via CO₂ laser IRMPD, water was seen to add to the complex. These results are consistent with high‐spin Mn²⁺ complexes.     

Collision induced dissociation of stored gold cluster ions

The stability of gold cluster ions Au _n ⁺ (2n23) has been investigated via collision induced dissociation in a Penning trap. Threshold energies and dissociation channels have been determined. The cluster stability exhibits a pronounced odd — even alternation: Clusters with an odd number of atoms,n, are more stable than the even-numbered ones. Enhanced stabilities are found for Au ₃ ⁺ , Au ₉ ⁺ , and Au ₁₉ ⁺ in accordance with the Clemenger-Nilsson and the deformed jellium model of delocalized valence electrons. Excited odd cluster ions withn15 predominantly decay by evaporation of dimers; all others decay by monomer evaporation. From the dissociation channels estimates of the binding energies are deduced.This publication comprises part of the thesis of St. Becker     

Quantum molecular interpretation of absorption spectra of small alkali metal clusters

The ab initio CI study of excited states of alkali metal clusters accounts for spectroscopical patterns obtained from the photodepletion spectra of the neutral or cationic species, predicts the excitation energies and transition intensities in the complete agreement with the measured quantities and permits an assignment of the cluster structures. The calculated optical spectra for various clusters with 4 and 8 valence electrons are compared: Na₄, Li₄, LiNa₃; Na₈ and Na ₉ ⁺ . A molecular interpretation of the rich spectra of tetramers as well as of the dominant intense transitions located at ～2.5–2.7 eV in the case of Na₈ and Na ₉ ⁺ with the weak fine structure shifted to the red is given.     

Fragmentation of clusters induced by collision with a solid surface: comparison of antimony and bismuth cluster ions

Mass-selected antimony cluster ions Sb _n ⁺ (n = 3-12) and bismuth cluster ions Bi _{ntn} ⁺ (n = 3-8) are allowed to collide with the surface of highly oriented pyrolytic graphite at energies up to 350 eV. The resulting fragment ions are analysed in a time-of-flight mass spectrometer. Two main fragmentation channels can be identified. At low impact energies both Sb _n ⁺ and Bi _n ⁺ cluster ions lose neutral tetramer and dimer units upon collision. Above about 150 eV impact energy Sb ₃ ⁺ becomes the predominant fragment ion of all investigated antimony clusters. The enhanced stability of these fragment clusters can be explained in the framework of the polyhedral skeletal electron pair theory. In contrast, Bi _n ⁺ cluster scattering leads to the formation of Bi ₃ ⁺ , Bi ₂ ⁺ and Bi+ with nearly equal abundances, if the collision energy exceeds 75 eV. The integral scattering yield is substantially higher in this case as compared to Sb _n ⁺ clusters.     

Hydration preferences for Mn4Ca cluster models of photosystem II: location of potential substrate-water binding sites

Density functional theory calculations are reported on a set of three model structures of the Mn₄Ca cluster in the water‐oxidizing complex of Photosystem II (PSII), which share the structural formula [CaMn₄C₉H₁₀N₂O₁₆]^q+ ? (H₂O)_n (q=?1, 0, 1, 2, 3; n=0–7). In these calculations we have explored the preferred hydration sites of the Mn₄Ca cluster across five overall oxidation states (S₀ to S₄) and all feasible magnetic‐coupling arrangements to identify the most likely substrate–water binding sites. We have also explored charge‐compensated structures in which the overall charge on the cluster is maintained at q=0 or +1, which is consistent with the experimental data on sequential proton loss in the real system. The three model structures have skeletal arrangements that are strongly reminiscent, in their relative metal‐atom positions, of the 2.9‐, 3.7‐, and 3.5 Å‐resolution crystal structures, respectively, whereas the charge states encompassed in our study correspond to an assignment of (Mn^III)₃Mn^II for S₀ and up to (Mn^IV)₃Mn^III for S₄. The three models differ principally in terms of the spatial relationship between one Mn (Mn(4)) and a generally robust Mn₃Ca tetrahedron that contains Mn(1), Mn(2), and Mn(3). Oxidation‐state distributions across the four manganese atoms, in most of the explored charge states, are dependent on details of the cluster geometry, on the extent of assumed hydration of the clusters, and in some instances on the imposed magnetic‐coupling between adjacent Mn atoms. The strongest water‐binding sites are generally those on Mn(4) and Ca. However, one structure type displays a high‐affinity binding site between Ca and Mn(3), the S‐state‐dependent binding‐energy pattern of which is most consistent with the substrate water‐exchange kinetics observed in functional PSII. This structure type also permits another water molecule to access the cluster in a manner consistent with the substrate–water interaction with the Mn cluster, seen in electron spin‐echo envelope modulation (ESEEM) studies of the functional enzyme in the S₀ and S₂ states. It also rationalizes the significant differences in hydrogen‐bonding interactions of the substrate water observed in the FTIR measurements of the S₁ and S₂ states. We suggest that these two water‐binding sites, which are molecularly close, model the actual substrate‐binding sites in the enzyme.     

Unusual stabilization of manganese(III) during the cooxidation of dimethylformamide and manganese(II) by chromium(VI)

The kinetics of the formation and decomposition of Mn^III have been investigated spectrophotometrically in acidic media at 25 °C. The complete rate law for Mn^III formation isCr^VI + DMF + Mn^II {H⁺} Mn^III + CO₂ + Me₂NH + Cr^III ... (1)Mn^III + DMF {H⁺} Mn^II + CO₂ + Me₂NH ... (2)expressed by k _obs1 = k ₁ k₁ K _a1[H⁺][DMFH⁺][Mn^II]/{1 + K _a1[H⁺]}. Mn^III reduction by DMF follows the rate law k _obs2 = k ₂ K _h[DMF][H⁺]²/{[H⁺] + K _h}. The above results are accounted for by a mechanism involving the intermediacy of Cr^IV.     

Gaussian density-functional study for small neutral (Al n ), positive (Al n + ) and negative (Al n − ) aluminium clusters (n=2–5)

The structures and properties of Al _n , Al _n ⁺ , Al _n ^– (n=1,5) clusters have been investigated by using the Linear Combination of Gaussian Type Orbitals (LCGTO) method, considering Local (LSD) and Non Local (NLSD) Spin Density Approximations and employing a Model Core Potential (MCP) that allows the explicit treatment of 3s ² 3p ¹ valence electrons. For each system different geometrical structures and electronic states have been considered. For Al₃, Al ₃ ⁺ , Al ₃ ^– the most stable geometry proved to be the equilateral triangle (D _3h ). Al₄ and Al ₄ ⁺ prefer the rhombus (D _2h ) structure, while the corresponding anion prefers the square (D _4h ) one. The trapezoidal form (C _2v ) is the most stable isomer for Al₅, Al ₅ ⁺ and Al ₅ ^– clusters. The analysis of vibrational frequencies shows that these structures are minima in the potential energy surface. The binding energies (D _e), the adiabatic ionization potentials (IP) and electron affinities (EA), the chemical potentials or absolute hardnesses () and electronegativities () have been computed. Results are in good agreement with the available experimental data and the previous high level theoretical computations.     

Kinetics and mechanism of the homogeneous reaction between some manganese(III)-Schiff base complexes and hydrogen peroxide in aqueous and sodium dodecyl sulphate solutions

Summary The kinetics of the reaction between H₂O₂ and some Schiff base complexes of Mn^III have been investigated in both aqueous and micellar sodium dodecyl sulphate (SDS) solution. The reaction rate is first order in both H₂O₂ and [complex], and inversely proportional to [H⁺]. The second-order rate constant increases in the sequence [Mn(salophen)(OAc)] > [Mn(salen)(OH₂)]-ClO₄ > [Mn(salen)(OAc)]H₂O, where salen = N,N-bis-(salicylidene)ethylenediamine and salophen = N,N-bis-(salicylidene)-o-phenylenediamine. At SDS concentrations below the critical micellar concentration, there is almost no effect on the rate of reaction whereas at higher concentrations the reaction rate increases slightly. A mechanism involving Mn^II and a peroxo intermediate is proposed.     

Ab initio investigation of possible lower-energy candidate structure for cationic water cluster (H2O) 12+ via particle swarm optimization method

Detecting the underlying performance of hydrated electrons and hydroxyl radicals in the cationic water cluster can greatly help to understand the inter reaction mechanism in the liquid water and aqueous solutions. Based on our previous (H₂O)₁₀⁺ research, we have paid attention to more problems of larger cationic clusters in this work, including the existence of hemibonded type, long-range correction functions, and hydrogen-bonded site analyses. The lower-energy structures of the cationic water cluster (H₂O)₁₂⁺ have been comprehensively explored, and more experienced functions are introduced to check the ground state and vibration spectrum. Unlike the configuration regularity of neutral (H₂O)₁₂ clusters and small cationic water clusters, those new-found structures for (H₂O)₁₂⁺ are inclined to adopt three dimension (3D) cage-like structures and the H₂O-OH₂ structure appears in the higher energy isomer. The calculation reveals that the lowest stable isomer is the 3D cage structure W14 predicted at MP2 level, which has not been reported yet. In the thermal simulation, structure transition from the cage-like to the ring-like occurs at T?>?≈256 K, and the two dimension (2D) ring-like structure occupies a dominant position at high temperature range. The infrared spectra explain that the difference of the spectra between the 2D net structures and 3D cage-structures is mainly caused by the weight fluctuation of single acceptor-single donor (AD), double acceptor-single donor (AAD), and single acceptor-double donor (ADD) sites in these isomers. This further gives a similarity relation between (H₂O)₁₂⁺ and H⁺(H₂O)₁₂ clusters in the shape of the network and spectral characteristics. By molecular orbitals and topological analysis, we find that the lone pair orbital on hydroxyl radical dominates the reactivity and stability of cationic system. The present research may be helpful for exploring the evolution law of the larger cationic water clusters in the future.

     

Density functional study of structural and electronic properties of maximum‐spin n+1Aun−1Ag clusters

The structures and relative stabilities of high‐spin ⁿ⁺¹Au_n?1Ag and ⁿAu_n?1Ag⁺ (n = 2–8) clusters have been studied with density functional calculation. We predicted the existence of a number of previously unknown isomers. Our results revealed that all structures of high‐spin neutral or cationic Au_n?1Ag clusters can be understood as a substitution of an Au atom by an Ag atom in the high‐spin neutral or cationic Au_n clusters. The properties of mixed gold–silver clusters are strongly sized and structural dependence. The high‐spin bimetallic clusters tend to be holding three‐dimensional geometry rather than planar form represented in their low‐spin situations. Silver atom prefers to occupy those peripheral positions until to n = 8 for high‐spin clusters, which is different from its position occupied by light atom in the low‐spin situations. Our theoretical calculations indicated that in various high‐spin Au_n?1Ag neutral and cationic species, ⁵Au₃Ag, ³AuAg and ⁵Au₄Ag⁺ hold high stability, which can be explained by valence bond theory. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Laser induced fission of C60 with kinetic energy release

A neutral C₆₀ fullerene beam is ionised by 308 nm laser pulses. For each cluster sizeC _n ⁺ , 0n60 of the typical bimodal mass distributions known from the literature [1] velocity distributions have been determined by a time of flight method. A consistent interpretation of the measured mean velocities is obtained when binary fission of the parent molecule is assumed to be responsible for the fragmentation patterns, the total kinetic energy release being 0.45±0.1 eV independent of fragment mass and of laser fluence.     

Synthesis and redox properties of bis-ferrocenylethynyl derivatives of bis(dimethylphosphinoethane)manganese

Paramagnetic Mn^II and Mn^III complexes containing two ferrocenylethynyl ligands were synthesized. Their redox reactions were studied by cyclic voltammetry and chemical methods. The structures of the resulting compounds were determined by IR, ¹H NMR, and ESR spectroscopy. The structure of the complex [(FcCC)₂Mn(dmpe)₂]⁺PF₆ ^– was established by X-ray diffraction analysis.