Photodissociation of iron oxide cluster cations

Iron oxide cluster cations, Fe(n)O(m)(+), are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. The mass spectrum exhibits a limited number of stoichiometries for each value of n, where m > or = n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic of a Nd:YAG laser. At either wavelength, multiple photon absorption is required to dissociate these clusters, which is consistent with their expected strong bonding. Cluster dissociation occurs via elimination of molecular oxygen, or by fission processes producing stable cation species. For clusters with n < 6, oxygen elimination proceeds until a terminal stoichiometry of n = m is reached. Clusters with this 1:1 stoichiometry do not eliminate oxygen, but rather undergo fission, producing smaller (FeO)n(+) species. The decomposition of larger clusters produces a variety of product cations, but those with the 1:1 stoichiometry are always the most prominent and these same species are produced repeatedly from different parent ions. These combined results establish that species of the form (FeO)n(+) have the greatest stability throughout these small iron oxide clusters.     

Photodissociation of yttrium and lanthanum oxide cluster cations

Transition metal oxide cations of the form M n O m (+) (M = Y, La) are produced by laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. Cluster oxides for each value of n form only a limited number of stoichiometries; MO(M2O3)x(+) species are particularly intense. Cluster cations are mass selected and photodissociated using the third harmonic (355 nm) of a Nd:YAG laser. Multiphoton excitation is required to dissociate these clusters because of their strong bonding. Yttrium and lanthanum oxides exhibit different dissociation channels, but some common trends can be identified. Larger clusters for both metals undergo fission to make certain stable cation clusters, especially MO(M2O3) x (+) species. Specific cations are identified to be especially stable because of their repeated production in the decomposition of larger clusters. These include M3O4(+), M5O7(+), M7O10(+), and M9O13(+), along with Y6O8(+). Density functional theory calculations were performed to investigate the relative stabilities and structures of these systems.     

Photodissociation of vanadium, niobium, and tantalum oxide cluster cations

Transition-metal oxide clusters of the form M(n)O(m) (+)(M=V,Nb,Ta) are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. Consistent with earlier work, cluster oxides for each value of n produce only a limited number of stoichiometries, where m>n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic of a Nd:YAG (yttrium aluminum garnet) laser. All of these clusters require multiphoton conditions for dissociation, consistent with their expected strong bonding. Dissociation occurs by either elimination of oxygen or by fission, repeatedly producing clusters having the same specific stoichiometries. In oxygen elimination, vanadium species tend to lose units of O(2), whereas niobium and tantalum lose O atoms. For each metal increment n, oxygen elimination proceeds until a terminal stoichiometry is reached. Clusters having this stoichiometry do not eliminate more oxygen, but rather undergo fission, producing smaller M(n)O(m) (+) species. The smaller clusters produced as fission products represent the corresponding terminal stoichiometries for those smaller n values. The terminal stoichiometries identified are the same for V, Nb, and Ta oxide cluster cations. This behavior suggests that these clusters have stable bonding networks at their core, but additional excess oxygen at their periphery. These combined results determine that M(2)O(4) (+), M(3)O(7) (+), M(4)O(9) (+), M(5)O(12) (+), M(6)O(14) (+), and M(7)O(17) (+) have the greatest stability for V, Nb, and Ta oxide clusters.     

Dehydrogenation of methanol by vanadium oxide and hydroxide cluster cations in the gas phase

Bare vanadium oxide and hydroxide cluster cations, V(m)O(n)+ and V(m)O(n-1) (OH)+ (m = 1-4, n = 1-10), generated by electrospray ionization, were investigated with respect to their reactivity toward methanol using mass spectrometric techniques. Several reaction channels were observed, such as abstraction of a hydrogen atom, a methyl radical, or a hydroxymethyl radical, elimination of methane, and adduct formation. Moreover, dehydrogenation of methanol to generate formaldehyde was found to occur via four different pathways. Formaldehyde was released as a free molecule either upon transfer of two hydrogen atoms to the cluster or upon transfer of an oxygen atom from the cluster to the neutral alcohol concomitant with elimination of water. Further, formaldehyde was attached to V(m)O(n)+ upon loss of H2 or neutral water to produce the cation V(m)O(n)(OCH(2))+ or V(m)O(n-1) (OCH(2))+, respectively. A reactivity screening revealed that only high-valent vanadium oxide clusters are reactive with respect to H2 uptake, oxygen transfer, and elimination of H2O, whereas smaller and low-valent cluster cations are capable of dehydrogenating methanol via elimination of H2. For comparison, the reactivity of methanol with the corresponding hydroxide cluster ions, V(m)O(n-1) (OH)+, was studied also, for which dominant pathways lead to both condensation and association products, i.e., generation of the ions V(m)O(n-1) (OCH(3))+ and V(m)O(n-1) (OH)(CH(3)OH)+, respectively.     

Gas-phase oxidation of isomeric butenes and small alkanes by vanadium-oxide and -hydroxide cluster cations

Bare vanadium-oxide and -hydroxide cluster cations (V(m)O(n)H(o)+, m = 2-4, n = 1-10, o = 0, 1) were generated by electrospray ionization in order to examine their intrinsic reactivity toward isomeric butenes and small alkanes using mass spectrometric techniques. Two of the major reactions described here concern the activation of C-H bonds of the alkene/alkane substrates resulting in the transfer of two hydrogen atoms and/or attachment of the dehydrogenated hydrocarbon to the cluster cations; these processes are classified as oxidative dehydrogenation (ODH) and dehydrogenation, respectively. For the dehydrogenation of butene, it evolved as a general trend that high-valent clusters prefer ODH resulting in the addition of two hydrogen atoms to the cluster concomitant with elimination of neutral butadiene, whereas low-valent clusters tend to add the diene with parallel loss of molecular hydrogen. Deuterium labeling experiments suggest the operation of a different reaction mechanism for V2O2(+) and V4O10(+) compared to the other cluster cations investigated, and these two cluster cations also are the only ones of the vanadium-oxide ions examined here that are able to dehydrogenate small alkanes. The kinetic isotope effects observed experimentally imply an electron transfer mechanism for the ion-molecule reactions of the alkanes with V4O10(+).     

Guided ion-beam studies of the reactions of Co(n)+ (n=2-20) with O2: cobalt cluster-oxide and -dioxide bond energies

The kinetic-energy dependence for the reactions of Co(n)+ (n=2-20) with O2 is measured as a function of kinetic energy over a range of 0 to 10 eV in a guided ion-beam tandem mass spectrometer. A variety of Co(m)+, Co(m)O+, and Co(m)O2+ (m < or = n) product ions is observed, with the dioxide cluster ions dominating the products for all larger clusters. Reaction efficiencies of Co(n)+ cations with O2 are near unity for all but the dimer. Bond dissociation energies for both cobalt cluster oxides and dioxides are derived from threshold analysis of the energy dependence of the endothermic reactions using several different methods. These values show little dependence on cluster size for clusters larger than three atoms. The trends in this thermochemistry and the stabilities of oxygenated cobalt clusters are discussed. The bond energies of Co(n)+-O for larger clusters are found to be very close to the value for desorption of atomic oxygen from bulk-phase cobalt. Rate constants for O2 chemisorption on the cationic clusters are compared with results from previous work on cationic, anionic, and neutral cobalt clusters.     

Photodissociation of cobalt and nickel oxide cluster cations

Cobalt and nickel oxide cluster cations, Co(x)O(y)(+) and Ni(x)O(y)(+), are produced by laser vaporization of metal rods in a pulsed nozzle cluster source and detected using time-of-flight mass spectrometry. The mass spectra show prominent stoichiometries of x = y for Co(x)O(y)(+) along with x = y and x = y - 1 for Ni(x)O(y)(+). The cluster cations are mass selected and multiphoton photodissociated using the third harmonic (355 nm) of a Nd:YAG laser. Although various channels are observed, photofragmentation exhibits two main forms of dissociation processes in each system. Co(x)O(y)(+) dissociates preferentially through the loss of O(2) and the formation of cobalt oxide clusters with a 1:1 stoichiometry. The Co(4)O(4)(+) cluster seems to be particularly stable. Ni(x)O(y)(+) fragments reveal a similar loss of O(2), although they are found to favor metal-rich fragments with stoichiometries of Ni(x)O(x-1). The Ni(2)O(+) fragment is produced from many parent ions. The patterns in fragmentation here are not nearly as strong as those seen for early or mid-period transition-metal oxides studied previously.     

On the iron oxide neutral cluster distribution in the gas phase. I. Detection through 193 nm multiphoton ionization

Iron oxide (FemOn) neutral clusters are generated in the gas phase through laser ablation of the metal and reaction with various concentrations of O2 in He. The mixture of expansion gas and neutral FemOn cluster species is expanded through a supersonic nozzle into a vacuum system, in which the clusters are ionized by an ArF excimer laser at 193 nm, and the ions are detected and identified in a time-of-flight mass spectrometer. In this report, the experimental parameters that influence the observed cluster distributions, such as ablation laser power, expansion pressure, vacuum system pressure, and 193 nm ArF ionization laser power, are explored. In the second paper in this series, the effect of the ionization laser wavelength (355 nm, 193 nm, 118 nm) on the observed cluster ion distribution is explored. The cluster ion distribution observed employing 193 nm laser ionization, is sensitive to the neutral cluster distribution as evidenced by the change in the observed time-of-flight mass spectra with changes in laser power, growth conditions, and expansion conditions. The thermodynamically stable neutral clusters for saturated O2 growth conditions are suggested to be of the forms FemOm, FemO(m+1), and FemO(m+2); which one of these series of neutral clusters is most stable depends on the size of the cluster. For m < 10, FemOm is the most stable neutral cluster series, for 10 < or = m < or = 20, FemO(m+1) is the most stable neutral cluster series, and for 21 < or = m < = 30, FemO(m+2) is the most stable neutral cluster series. Some neutral cluster fragmentation is clearly present for 193 nm ionization due to multiphoton absorption in both the neutral and ionic cluster species.     

On the iron oxide neutral cluster distribution in the gas phase. II. Detection through 118 nm single photon ionization

Neutral clusters of iron oxide are created by laser ablation of iron metal and subsequent reaction of the gas phase metal atoms, ions, clusters, etc., with an O2/He mixture. The FemOn clusters are cooled in a supersonic expansion and detected and identified in a time-of-flight mass spectrometer following laser ionization at 118 nm (10.5 eV), 193 nm (6.4 eV), or 355 nm (3.53 eV) photons. With 118 nm radiation, the neutral clusters do not fragment because single photon absorption is sufficient to ionize all the clusters and the energy/pulse is approximately 1 microJ. Comparison of the mass spectra obtained at 118 nm ionization (single photon) with those obtained at 193 nm and 355 nm ionization (through multiphoton processes), with regard to intensities and linewidths, leads to an understanding of the multiphoton neutral cluster fragmentation pathways. The multiphoton fragmentation mechanism for neutral iron oxide clusters during the ionization process that seems most consistent with all the data is the loss of one or two oxygen atoms. In all instances of ionization by laser photons, the most intense features are of the forms FemOm+, FemO(m+1)+, and FemO(m+2)+, and this strongly suggests that, for a given m, the most prevalent neutral clusters are of the forms FemOm, FemO(m+1), and FemO(m+2). As the value of m increases, the more oxygen rich neutral clusters appear to increase in stability.     

Formation, photodissociation and structure of chromium/phosphorus binary cluster ions

Chromium/phosphorus binary cluster ions, [Cr(n)P(m)](+/-), produced by laser (532nm) ablation on a tablet of well-mixed chromium and red phosphorus powder, were studied with a home-built tandem time-of-flight (TOF) mass spectrometer. The clusters thus formed are mostly rich in phosphorus. There is an odd-even oscillation in the intensity of the [CrP(m)](+) series, i.e. the mass peaks of even m are higher than those of odd m. The peaks of [CrP(4)](+) and [CrP(8)](+) are especially prominent, which may be ascribed to the specific stability of P(4) sub-structures. There are also some intense peaks in the spectrum assigned to [Cr(3)P(8)](+), [Cr(4)P(9)](+), [Cr(5)P(11)](+), [Cr(6)P(12)](+), [Cr(8)P(14)](+) clusters, etc., which have stable compositions. The stability of these species is consistent with a simple qualitative electronic structure model, in which the valence electrons of P are filled into the d orbitals of Cr. The photodissociation of some cluster ions was also studied. DFT calculations were performed on three small cluster ions to provide some insight into their structures. Copyright 2000 John Wiley & Sons, Ltd.     

On the copper oxide neutral cluster distribution in the gas phase: detection through 355 nm and 193 nm multiphoton and 118 nm single photon ionization

The distribution of neutral copper oxide clusters in the gas phase created by laser ablation is detected and characterized through time-of-flight mass spectroscopy (TOFMS). The neutral copper oxide clusters are ionized by two different approaches: Multiphoton absorption of 355 and 193 nm radiation; and single photon absorption of 118 nm radiation. Based on the observed cluster patterns as a function of experimental conditions (e.g., copper oxide or metal sample, ablation laser power, expansion gas, etc.) and on the width of the TOFMS features, one can uncover the true neutral cluster distribution of CumOn species following laser ablation of the sample. Ablation of a metal sample generates only small neutral CumOn clusters for m less, similar 4 and n approximately 1, 2. Ablation of copper oxide samples generates neutral clusters of the form CumOm (m < or = 4) and CumO(m-1) (m > 4). These clusters are directly detected without fragmentation using single photon, photoionization with 118 nm laser radiation. Using 355 and 193 nm multiphoton ionization, the observed cluster ions are mostly of the form Cu2mOm+ for 4 < or = m < or = 10 (193 nm ionization) and CumO1,2 (355 nm ionization) for copper oxide samples. Neutral cluster fragmentation due to multiphoton processes seems mainly to be of the form CumO(m,m-1) --> CumO(m/2,m/2+1). Neutral cluster growth mechanisms are discussed based on the cluster yield from different samples (e.g., Cu metal, CuO powder, and Cu2O powder).     

On the titanium oxide neutral cluster distribution in the gas phase: Detection through 118 nm single-photon and 193 nm multiphoton ionization

Titanium oxide clusters are generated in a supersonic expansion by laser ablation of the metal and reaction with oxygen (0.1-6%) in He expansion gas. Mass spectra of the titanium oxide clusters are observed by photoionization with lasers of three different wavelengths: 118, 193, and 355 nm. Only the 118 nm (10.5 eV) light can ionize Ti(m)O(n) neutral clusters without fragmentation. Both the 193 nm (6.4 eV) and 355 nm (3.5 eV) multiphoton ionization cause fragmentation of the neutral clusters during the ionization process and, thus, can complicate the determination of the stable neutral Ti(m)O(n) gas-phase species. Employing 118 nm single-photon ionization and line-width data, the Ti(m)O(2m) and Ti(m)O(2m+1) series are found to be the most stable neutral cluster species for high oxygen content in the expansion gas. Fragmentation during the multiphoton ionization process for 193 nm light yields the cluster ions Ti(m)O(2m-1,-2)+. These ions are formed by the loss of one or two oxygen atoms from Ti(m)O(2m,2m+1) neutral species. The dominant cluster growth process is suggested to be through the addition of TiO2 species. For low oxygen content (<2%) in the expansion gas, oxygen-deficient clusters of the form Ti(m)O(2m-1,-2) are also observed. These latter series are not fragmented by the 193 nm ionization process.     

Experimental and theoretical studies of reactions of neutral vanadium and tantalum oxide clusters with NO and NH3

Reactions of neutral vanadium and tantalum oxide clusters with NO, NH(3), and an NO/NH(3) mixture in a fast flow reactor are investigated by time of flight mass spectrometry and density functional theory (DFT) calculations. Single photon ionization through a 46.9 nm (26.5 eV) extreme ultraviolet (EUV) laser is employed to detect both neutral cluster distributions and reaction products. Association products VO(3)NO and V(2)O(5)NO are detected for V(m)O(n) clusters reacting with pure NO, and reaction products, TaO(3,4)(NO)(1,2), Ta(2)O(5)NO, Ta(2)O(6)(NO)(1-3), and Ta(3)O(8)(NO)(1,2) are generated for Ta(m)O(n) clusters reacting with NO. In both instances, oxygen-rich clusters are the active metal oxide species for the reaction M(m)O(n)+NO→M(m)O(n)(NO)(x). Both V(m)O(n) and Ta(m)O(n) cluster systems are very active with NH(3). The main products of the reactions with NH(3) result from the adsorption of one or two NH(3) molecules on the respective clusters. A gas mixture of NO:NH(3) (9:1) is also added into the fast flow reactor: the V(m)O(n) cluster system forms stable, observable clusters with only NH(3) and no V(m)O(n)(NO)(x)(NH(3))(y) species are detected; the Ta(m)O(n) cluster system forms stable, observable mixed clusters, Ta(m)O(n)(NO)(x)(NH(3))(y), as well as Ta(m)O(n)(NO)(x) and Ta(m)O(n)(NH(3))(y) individual clusters, under similar conditions. The mechanisms for the reactions of neutral V(m)O(n) and Ta(m)O(n) clusters with NO/NH(3) are explored via DFT calculations. Ta(m)O(n) clusters form stable complexes based on the coadsorption of NO and NH(3). V(m)O(n) clusters form weakly bound complexes following the reaction pathway toward end products N(2)+H(2)O without barrier. The calculations give an interpretation of the experimental data that is consistent with the condensed phase reactivity of V(m)O(n) catalyst and suggest the formation of intermediates in the catalytic chemistry.     

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.     

Enhancement of ammonia dehydrogenation by introduction of oxygen onto cobalt and iron cluster cations

Reactions of oxygen-chemisorbed cobalt and iron cluster cations (Co(n)O(m)(+) and Fe(n)O(m)(+); n = 3-6, m = 1-3) with an NH(3) molecule have been investigated in comparison with their bare metal cluster cations at a collision energy of 0.2 eV by use of a guided ion beam tandem mass spectrometer. We have observed three kinds of reaction products, which come from NH(3) chemisorption with and without release of a metal atom from the cluster and dehydrogenation of the chemisorbed NH(3). Reaction cross sections and branching fractions are strongly influenced by the number of oxygen atoms introduced onto the metal clusters. Oxygen-chemisorbed metal clusters with particular compositions such as Co(4)O(+), Co(5)O(2)(+), and Fe(5)O(2)(+) are extremely reactive for NH(3) dehydrogenation, whereas Co(4)O(2)(+) and Fe(4)O(2)(+) exhibit high reactivity for NH(3) chemisorption with metal release. The enhancement of dehydrogenation for specific compositions can be interpreted in terms of competition between O-H and neighboring Co-H (or Fe-H) formation.     

Stable copper-tin cluster compositions from high-temperature annealing

Copper-doped tin clusters can be thermally annealed to much more stable compositions with a substantially higher copper/tin ratio. The annealed clusters are only prominent over a narrow range of compositions: CuSn(10-15)+, Cu2Sn(12-18)+, Cu3Sn(15-21)+, Cu4Sn(18-(24)+, and Cu5Sn(21-(27)+. These compositions are close to those found for W(m)Si(n)+ clusters, raising the possibility that the Cu(m)Sn(n)+ clusters have core-shell geometries like those proposed for the W(m)Si(n)+ clusters. Increasing the number of copper atoms causes a change in the dissociation pattern from the fission processes that are characteristic of semiconductor clusters to the expulsion of individual atoms, which usually occurs for metal clusters. The change in the fragmentation pattern may result because the clusters rich in copper melt before they dissociate, while the pure tin clusters dissociate directly from a solidlike phase.     

H2 adsorption on 3d transition metal clusters: a combined infrared spectroscopy and density functional study

The adsorption of H2 on a series of gas-phase transition metal (scandium, vanadium, iron, cobalt, and nickel) clusters containing up to 20 metal atoms is studied using IR-multiple photon dissociation spectroscopy complemented with density functional theory based calculations. Comparison of the experimental and calculated spectra gives information on hydrogen-bonding geometries. The adsorption of H2 is found to be exclusively dissociative on Sc(n)O+, V(n)+, Fe(n)+, and Co(n)+, and both atomic and molecularly chemisorbed hydrogen is present in Ni(n)H(m)+ complexes. It is shown that hydrogen adsorption geometries depend on the elemental composition as well as on the cluster size and that the adsorption sites are different for clusters and extended surfaces. In contrast to what is observed for extended metal surfaces, where hydrogen has a preference for high coordination sites, hydrogen can be both 2- or 3-fold coordinated to cationic metal clusters.     

C4H5N-(NH3)n氢键团簇的多光子电力与从头计算

在３５５和５３２ｎｍ激光波长下用ＴＯＦ质谱仪研究了Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ系列氢键团簇体系的多光子电离,实验发现,两波长下除了得到一系列团簇离子Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ＾＋外,还观测到一系列质子化产物Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ－Ｈ＾＋,这些质子化产物来自于光电离过程中团簇内部的质子转移反应;Ｃ４Ｈ５Ｎ－（ＮＨ３）ｎ＾＋系列离子出现反常强度变化,即Ｃ４Ｈ５Ｎ－（ＮＨ３）２＾＋离子强度较Ｃ４Ｈ５Ｎ－（Ｎ     

铅、硫团簇的形成、反应与光解

用激光直接溅射和串级溅射两种方法产生铅／硫二元团簇,并用串级飞行时间质谱仪研究了二元团簇的组份及光解规律,用激光直接溅射铜＋硫混合样品时,组成为PbnSn-1 和PbnSn-的团簇丰度最大,是二元团簇的结构骨架和稳定组份,而用激光串级溅射铅样品和硫样品,通过铅团簇与硫团簇的反应,则可得到PbnSm (n=1-3,m=0-9)和PbnSm-(n=1-7,m=0-9)。这两种二元团簇的产生方法对应两种不同的团簇形成机理。     

氰化钾团簇的结构和形成机理研究

利用激光气化铁氰化钾或亚铁氰化钾并利用飞行时间质谱检测方法对氰化钾团簇的形成机理进行了研究，结果发现：团簇正离子可归属为［Ｋ（ＫＣＮ）＿ｎ］￣＋，ｎ＝０～３７，它们的幻数为ｎ＝４、１３、２２、３７；团族负离子可归属为［（ＫＣＮ）＿ｎＣＮ］￣－＝，ｎ＝０～１３，它们的幻数为ｎ＝４、１３。这些幻数与氯化钠等碱金属卤化物团簇体系完全一致。这表明：它们的团簇结构应该是相同的，即１×３×３（ｎ＝４）、３×３×３（ｎ＝１３）、３×３×５（ｎ＝２２）、３×５×５（ｎ＝３７）结构。因此氰化钾晶体的初期形成过程也应采取ＮａＣｌ型结构的增长途径。在激光气化产生的等离子体中，正、负离子与中性团簇的碰撞增长反应、正离子与负离子的复合反应以及团簇的亚稳态解离反应造成了团簇离子的不同丰度分布。氰化钾团簇中稳定立方体结构的产生决定了幻数的出现。