Gas-phase Clusters Research Articles

Rhodium chemistry: A gas phase cluster study.

Due to the extraordinary catalytic activity in redox reactions, the noble metal, rhodium, has substantial industrial and laboratory applications in the production of value-added chemicals, synthesis of biomedicine, removal of automotive exhaust gas, and so on. The main drawback of rhodium catalysts is its high-cost, so it is of great importance to maximize the atomic efficiency of the precious metal by recognizing the structure-activity relationship of catalytically active sites and clarifying the root cause of the exceptional performance. This Perspective concerns the significant progress on the fundamental understanding of rhodium chemistry at a strictly molecular level by the joint experimental and computational study of the reactivity of isolated Rh-based gas phase clusters that can serve as ideal models for the active sites of condensed-phase catalysts. The substrates cover the important organic and inorganic molecules including CH4, CO, NO, N2, and H2. The electronic origin for the reactivity evolution of bare Rhx q clusters as a function of size is revealed. The doping effect and support effect as well as the synergistic effect among heteroatoms on the reactivity and product selectivity of Rh-containing species are discussed. The ingenious employment of diverse experimental techniques to assist the Rh1- and Rh2-doped clusters in catalyzing the challenging endothermic reactions is also emphasized. It turns out that the chemical behavior of Rh identified from the gas phase cluster study parallels the performance of condensed-phase rhodium catalysts. The mechanistic aspects derived from Rh-based cluster systems may provide new clues for the design of better performing rhodium catalysts including the single Rh atom catalysts.

Multi-structural feasibility in benzonitrile solvent through the multi hot-potential centers

The small organic molecules involving −CN group often constitute the building block of the biological systems and liquid solvents of strong dipole moment appreciated for organic synthesis. Among them, benzonitrile liquid has been proposed to be used as a co-solvent with green chemistry ionic liquids. In the first part of the series of researches, we present the study of benzonitrile clusters (up to tetramer) in gas and liquid phase (PCM) by density functional theory. We focus on unraveling and characterizing the interactions effective in the liquid benzonitrile, where dipole-dipole interaction has been already known as the majorly influential. By including clusters up to tetramers and studying their binding energies, identifying hydrogen bondings, verifying the possible (energy minima) structure of each cluster, elucidating and confirming the nature of hydrogen bonding (using AIM and NBO methods), assigning the stretching modes and shift in frequencies of C≡N group (IR Spectrum), and the thermodynamics stabilities, it is found quantitatively that hydrogen bondings, in addition to the dipole-dipole interaction already claimed as the main intermolecular interaction, play roles chiefly in stabilizing the clusters.

Calculating Reliable Gibbs Free Energies for Formation of Gas-Phase Clusters that Are Critical for Atmospheric Chemistry: (H2SO4)3.

The effects of atmospheric aerosols on our climate are one of the biggest uncertainties in global climate models. Calculating the pathway for the formation of pre-nucleation clusters that become aerosols is challenging, requiring a comprehensive analysis of configurational space and highly accurate Gibbs free energy calculations. We identified a large set of minimum energy configurations of (H2SO4)3 using a sampling technique based on a genetic algorithm and a stepwise density functional theory (DFT) approach and computed the thermodynamics of formation of these configurations with more accurate wavefunction-based electronic energies computed on the DFT geometries. The DLPNO-CCSD(T) methods always return more positive energies compared to the DFT energies. Within the DLPNO-CCSD(T) methods, extrapolating to the complete basis set limit gives more positive free energies compared to explicitly correlated single-point energies. The CBS extrapolation was shown to be robust as both the 4-5 inverse polynomial and Riemann zeta function schemes were within chemical accuracy of one another.

Reversible Hydration of α-Dicarbonyl Compounds from Ab Initio Metadynamics Simulations: Comparison between Pyruvic and Glyoxylic Acids in Aqueous Solutions.

Glyoxylic and pyruvic oxoacids are widely available in the atmosphere as gas-phase clusters and particles or in wet aerosols. In aqueous conditions, they undergo interconversion between the unhydrated oxo and gem-diol forms, where two hydroxyl groups replace the carbonyl group. We here examine the hydration equilibrium of glyoxylic and pyruvic acids with first-principles simulations in water at ambient conditions using ab initio metadynamics to reconstruct the corresponding free-energy landscapes. The main results are as follows: (i) our simulations reveal the high conformational diversity of these species in aqueous solutions. (ii) We show that gem-diol is strongly favored in water compared to its oxo counterpart by 29 and 16 kJ/mol for glyoxylic and pyruvic acids, respectively. (iii) From our atomic-scale simulations, we present new insights into the reaction mechanisms with a special focus on hydrogen-bond arrangements and the electronic structure of the transition state.

Volatile molecule chooses to cooperate.

Carbon dioxide molecules help toluene form gas-phase clusters through non-covalent interactions.

Hydration and Ion-Pair Formation of NaNO3(aq): A Vibrational Spectroscopic and Density Functional Theory Study.

Qualitative and quantitative Raman and infrared measurements on sodium nitrate (NaNO3) solutions have been carried out over a wide concentration range (5.56 × 10-6-7.946 mol/L) in water and heavy water. The Raman spectra were measured from 4000 cm-1 to low wavenumbers at 45 cm-1. Band fit analysis on the profile of the 1047 cm-1 band, ν1(a) measured at high resolution at 0.90 cm-1 produced a small contribution at 1027 cm-1 of the isotopomer N16O218O(aq). The effect of solute concentration on the Raman and infrared bands has been systematically recorded. Extrapolation of the experimental data resulted in values for all the nitrate bands of the "free", i.e., fully hydrated (aq). However, even in dilute solutions, the vibrational symmetry of the hydrated (aq) is broken and the antisymmetric N-O stretch, which is degenerate for the isolated anion, is split by 56 cm-1. At concentrations >2.5 mol/L, direct contact between Na+ and was observed and accompanied by large band parameter changes. DFT calculations on (H2O)n (n = 1-3) led to optimized geometries and vibrational frequencies which reproduced the measured ones within an accuracy of 1%. A hydrated gas phase species Na+(H2O)10 was optimized resulting in the geometry and symmetry of the nitrate, which is bound in an antisymmetric bidentate fashion with the nitrate possessing C1. The ν1 Na+(OH2) breathing mode in aqueous solution appears at 189 cm-1, whereas in heavy water, ν1 Na+(OD2) is shifted to 175.6 cm-1 due to the isotope effect. DFT calculations on hydrated Na+(OH2)n gas phase clusters provided realistic Na+ hydrate structures with n = 4 and 5, which resembled the measured frequency of ν1 Na+ OH2 mode quite well. Quantitative Raman analysis employing the symmetric stretching band, ν1(a) , has been carried out down to concentrations as low as 5.56 × 10-6 mol/L. The in-plane deformation mode ν4(e') in the Raman scattering at higher concentrations has been used as an indicator band for directly coordinated .

Consecutive methane activation mediated by single metal boride cluster anions NbB4.

Cleavage of all C-H bonds in two methane molecules by gas-phase cluster ions at room temperature is a challenging task. Herein, mass spectrometry and quantum chemical calculations have been used to identify one single metal boride cluster anions NbB4- that can activate eight C-H bonds in two methane molecules and release one H2 molecule each time under thermal collision conditions. In these consecutive reactions, the loaded Nb atoms and the support B4 units play different roles but act synergistically to activate CH4, which is responsible for the interesting reactivity of NbB4-. Moreover, there are some mechanistic differences in these two reactions, including the mechanisms for the first C-H bond activation steps, dihydrogen desorption sites, and major electron donors. This study shows that non-noble metal boride species are reactive enough to facilitate thermal C-H bond cleavages, and boron-based materials may be one kind of potential support material facilitating surface hydrogen transport.

Dipole moment enhanced π-π stacking in fluorophenylacetylenes is carried over from gas-phase dimers to crystal structures propagated through liquid like clusters.

The aggregates of monofluorinated phenylacetylenes in the gas-phase, investigated using the IR-UV double resonance spectroscopic method in combination with extensive structural search and electronic structure calculations, reveal the formation of liquid-like clusters with a π-stacked dimeric core. The structural assignment based on the IR spectra in the acetylenic and aromatic C-H stretching regions suggests that, unlike the parent non-fluorinated phenylacetylene, the substitution of a F atom on the phenyl ring increases the dipole moment, leading to robustness in the formation of a ππ stacked dimer, which propagates incorporating C-Hπ_{Ar/Ac} and C-HF interactions involving both acetylenic and aromatic C-H groups. The structural evolution of fluorophenylacetylene aggregates in the gas phase shows marginal effects due to fluorine atom position on the phenyl ring, with substitution in the para-position tending towards phenylacetylene. The present study signifies that the ππ stacked dimers act as a nucleus for the growth of higher clusters to which other molecular units are added predominantly via the {Ar}_C-Hπ_{Ar} type of interaction and the dominant interactions present in the crystal structures gradually emerge with increasing cluster size. Based on these features, gas-phase clusters of fluorophenylacetylene are hypothesized as "liquid-like clusters" acting as intermediates in the generation of various polymorphic forms starting from a ππ stacked dimer as the core molecular unit.

Generation of Multiply Charged Argon Ions in Nanosecond Laser Field Ionization of Argon Clusters.

Zhang and co-workers ( J. Phys. Chem. Lett. 2020, 11, 1100-1105) have recently reported results of experiments involving irradiation of argon clusters doped with bromofluorene chromophores by nanosecond-long pulses of 532 nm laser light. Multiply charged ions of atomic argon (Arn+, 1 ≤ n ≤ 7) and carbon (Cn+, 1 ≤ n ≤ 4) are observed, which are sought to be rationalized using an evaporation model. The distinguishing facet of exploding clusters being progenitors of energetic ions and electrons constitutes the key driver for contemporary research in laser-cluster interactions; it is, therefore, important to point out inconsistencies that are intrinsic to the model of Zhang and co-workers. In light of similar reports already in the literature, we show that their model is of limited utility in describing the dynamics that govern how fast, multiply charged atomic ions result from laser irradiation of gas-phase clusters. We posit that it is plasma behavior that underpins cluster heating and cluster explosion dynamics.

Decoding the 2D IR spectrum of the aqueous proton with high-level VSCF/VCI calculations

The aqueous proton is a common and long-studied species in chemistry, yet there is currently intense interest devoted to understanding its hydration structure and transport dynamics. Typically described in terms of two limiting structures observed in gas-phase clusters, the Zundel H5O2 + and Eigen H9O4 + ions, the aqueous structure is less clear due to the heterogeneity of hydrogen bonding environments and room-temperature structural fluctuations in water. The linear infrared (IR) spectrum, which reports on structural configurations, is challenging to interpret because it appears as a continuum of absorption, and the underlying vibrational modes are strongly anharmonically coupled to each other. Recent two-dimensional IR (2D IR) experiments presented strong evidence for asymmetric Zundel-like motifs in solution, but true structure-spectrum correlations are missing and complicated by the anharmonicity of the system. In this study, we employ high-level vibrational self-consistent field/virtual state configuration interaction calculations to demonstrate that the 2D IR spectrum reports on a broad distribution of geometric configurations of the aqueous proton. We find that the diagonal 2D IR spectrum around 1200 cm-1 is dominated by the proton stretch vibrations of Zundel-like and intermediate geometries, broadened by the heterogeneity of aqueous configurations. There is a wide distribution of multidimensional potential shapes for the proton stretching vibration with varying degrees of potential asymmetry and confinement. Finally, we find specific cross peak patterns due to aqueous Zundel-like species. These studies provide clarity on highly debated spectral assignments and stringent spectroscopic benchmarks for future simulations.

Substitution of O with a Single Au Atom as an Electron Acceptor in Al Oxide Clusters.

Al atoms generally adopt the +3 oxidation state and form stoichiometric oxides such as Al2O3 in the bulk phase. Among small cationic gas-phase clusters, near-stoichiometric clusters such as Al3O4+, Al3O5+, Al4O6+, Al4O7+, Al5O7+, and Al5O8+ have been readily generated in experimental studies. However, when a single Au atom was included in the clusters, oxygen-deficient clusters such as AuAl4O5+ were formed in high abundance; in these clusters, the Au atom accepted electron density from the Al atoms. The geometrical structures and atomic charges in the clusters suggest that a single Au atom can substitute for O atoms in Al oxide clusters. This propensity originates from the high electron and low oxygen affinities, which, together, constitute an unusual property of Au.

Identification and quantification of leucine and isoleucine residues in peptides using photoexcited tryptophan.

The molecular recognition ability of tryptophan (Trp) for isomeric amino acids, such as leucine (Leu) and isoleucine (Ile), and isomeric amino acid-containing dipeptides, such as Leu-Gly, Ile-Gly, Gly-Leu, and Gly-Ile (where Gly denotes glycine), was investigated using a tandem mass spectrometer equipped with an electrospray ionization source and cold ion trap. The ultraviolet photodissociation spectra of the cold gas-phase clusters of Leu and Ile with Na+Trp in the wavelength range of 265-290nm revealed that the relative intensities of Leu and Ile were only different in the wavelength range of 265-273nm; however, no differences in the relative intensities were observed when the wavelength exceeded 274nm. The molecular recognition ability of photoexcited Trp was used for the identification and quantification of Leu and Ile in dipeptides in solution. The mole fractions of Leu and Ile in dipeptides could be determined from the abundances observed in a single product ion spectrum of the cold gas-phase clusters of dipeptides with Na+Trp.

Intrazeolite CO Methanation by Small Ruthenium Carbonyl Complexes: Translation from Free Clusters into the Cage

AbstractCatalytic CO methanation represents an important reaction to improve the feed gas quality for hydrogen fuel cells. Previously, the large potential of small bare and ligated ruthenium clusters as highly selective and active catalysts has been shown by employing gas phase clusters as model systems. Now, density functional theory (DFT) calculations are employed to demonstrate the possibility to translate the gas phase CO methanation reaction mediated by a ligated Ru4(CO)13H2+ complex into the framework of a ZSM‐5 zeolite. Such a translation, manifested by a reaction pathway which is mechanistically and energetically similar to the gas phase analogue, is possible since the zeolite framework does not influence the reactive center. Furthermore, we reveal the important role of the CO ligand environment in protecting the Ru4+ metal core from formation of bonds with the zeolite and in the creation of the reactive center by promoting the cooperatively enhanced adsorption and dissociation of H2.

Gas-Phase Deposition of Gold Nanoclusters to Produce Heterogeneous Glycerol Oxidation Catalysts

Gold nanoparticles prepared by colloidal methods are effective catalysts for selective glycerol oxidation under basic conditions. Large-scale synthesis of catalysts by wet chemical methods leads to large amounts of waste and can result in polymer or salt residues remaining on the catalyst. In contrast, gas-phase cluster deposition (cluster beam deposition) offers a solvent-free method to synthesize controlled nanoparticles/clusters. We show that the deposition of bare gas-phase gold clusters onto carbon powder leads to a catalyst comparable to that prepared by colloidal methods. This shows the feasibility of the synthesis method to produce oxidation catalysts with reduced waste.

Hydrogenated gold clusters from helium nanodroplets: displacement of H2 by H2O

Cationic clusters of gold, containing up to 8 atoms, and decorated with molecular hydrogen and water, were investigated with mass spectrometry. The clusters were grown as neutrals in superfluid helium nanodroplets that were ionized by electron impact. The resulting gas phase cluster cations exhibit magic sizes corresponding to the number of H2 molecules that form the first solvation layer, consistent with previous findings. The presence of water is found to efficiently displace hydrogen, one H2 molecule for each H2O. Our calculations show that the binding energy of water to the charged gold clusters is about twice as large as for hydrogen, though this depends on the charge of the clusters. This suggests that residual water could reduce the efficiency for metal particles to chemically store hydrogen gas, a promising technique for hydrogen fuel storage.Graphical abstract

Endohedral Plumbaspherenes of the Group 9 Metals: Synthesis, Structure and Properties of the [M@Pb12]3− (M=Co, Rh, Ir) Ions

The icosahedral [M@Pb12 ]3- (M=Co(1), Rh(2), Ir(3)) cluster ions were prepared from K4 Pb9 and Co(dppe)Cl2 (dppe=1,2-bis(diphenylphosphino)ethane)/[Rh(PPh3 )3 Cl]/[Ir(cod)Cl]2 (cod=1,5-cyclooctadiene), respectively, in the presence of 18-crown-6/ 2,2,2-cryptand in ethylenediamine/toluene solvent mixtures. The [K(2,2,2-cryptand)]+ salt of 1 and the [K(18-crown-6)]+ salt of 3 were characterized via X-ray crystallography; the ions 1 and 3 are isostructural and isoelectronic to the [Rh@Pb12 ]3- (2) ion as well as to the group 10 clusters [M'@Pb12 ]2- (M'=Ni, Pd, Pt). The ions are all 26-electron clusters with near perfect icosahedral Ih point symmetry. Clusters 1-3 show record downfield 207 Pb NMR chemical shifts due to σ-aromaticity of the cluster framework. Calculated and observed 207 Pb NMR chemical shifts and 207 Pb-x M J-couplings (x M=59 Co, 103 Rh, 193 Ir) are in excellent agreement and DFT analysis shows that the variations of 207 Pb NMR chemical shifts for the [M@Pb12 ]2, 3- ions (M=Co, Rh, Ir, Ni, Pd, Pt) are mainly governed by the perpendicularly oriented σ11 component of the chemical shift anisotropy tensor. The laser desorption ionization time-of-flight (LDI-TOF) mass spectra contain the molecular ions as well as several new gas phase clusters derived from the parents. The DFT-minimized structures of these ions are described.

Wavelength dependence of chiral recognition using ions between photoexcited tryptophan and sugars

The reactivity of cold gas-phase clusters was investigated as a model for chemical evolution in interstellar molecular clouds. Chiral recognition using ions between amino acids and sugars was examined by mass spectrometry and ultraviolet spectroscopy measurements of gas-phase tryptophan (Trp) enantiomers hydrogen bonded with methyl-α-d-glucoside in Na+-containing or protonated forms at 8 K. The chiral recognition mechanism between Trp and the glucoside changed depending on the photoexcitation wavelength: the enantiomer-selective reactions at 265–280 nm and the electronic structure of Trp at 280–290 nm. The attachment of Na+ to d-Trp and the Cα–Cβ bond cleavage of d-Trp were the enantiomer-selective reactions in the Na+-containing and protonated clusters, respectively. The wavelength dependences of the enantiomer-selective reactions were similar between the Na+-containing and protonated clusters. This is because the enantiomer-selective reactions were triggered by photoinduced electron transfer from the indole ring to the carboxyl group of Trp in the clusters.

Palladium nanoparticles supported by three-dimensional freestanding electrodes for high-performance methanol electro-oxidation

Palladium (Pd) nanoparticles (NPs) prepared by gas phase cluster deposition demonstrated excellent electrocatalytic activity. Herein, a series of Pd NPs modified freestanding electrodes with a super clean surface and easy repeating process for methanol oxidation reaction is reported. Pd NPs with different coverage were deposited on Ni foams and three-dimensional graphene-Ni foams, respectively. Owning to the special three-dimensional structure of Ni foam, the Pd NPs-Ni foam composite exhibited remarkable activity and unusually long-term stability for methanol electro-oxidation. The introduced three-dimensional graphene prepared by conventional chemical vapour deposition improved the electrocatalytic performance. The results can be attributed to the Pd NPs with high electrochemical activity and unique properties for three-dimensional supports.

O2 activation by AuAg clusters on a defective (100)MgO surface

In the present work, we discuss the electronic properties of supported dispersed bimetallic clusters with respect to their size, geometry, and Aun/Agm (n + m = 6) composition. We have studied with supercell-density functional theory calculations the role of the charge transfer from the MgO defective support toward the cluster in the activation of O2 by AunAgm clusters. We first considered gas-phase clusters with different atomic compositions; then, we deposited all of them on a pristine (100)MgO surface and finally on a more realistic (100)MgO F-center. We performed a global and unrestricted search of the (cluster + surface) geometry. The Mexican enhanced genetic algorithm has been used to exhaustively explore the potential energy surface. Our results show that O2 activation depends on the Aun/Agm ratio. It has been found that both metals involved play different and important roles toward (a) the actual O2 dissociation and (b) weakening of the oxygen-cluster bond, which, in turn, may promote the possibility of a catalytic process to take place, such as the oxidation process of CO and NOx among others.

Perfect cubic La-doped boron clusters La6&[La@B24]+/0 as the embryos of low-dimensional lanthanide boride nanomaterials.

La-doped boron nanoclusters have received considerable attention due to their unique structures and bonding. Inspired by recent experimental observations of the inverse sandwich D8h La2B8 (1) and triple-decker C2v La3B14− (2) and based on extensive global searches and first-principles theory investigations, we present herein the possibility of the perfect cubic La-doped boron clusters Oh La6&[La@B24]+ (3, 1A1g) and Oh La6&[La@B24] (4, 2A2g) which appear to be the embryos of the metallic one-dimensional La10B32 (5) nanowire, two-dimensional La3B10 (6) nanosheet, and three-dimensional LaB6 (7) nanocrystal, facilitating a bottom-up approach to build cubic lanthanide boride nanostructures from gas-phase clusters. Detailed molecular orbital and bonding analyses indicate that effective (d–p)σ, (d–p)π and (d–p)δ covalent coordination interactions exist in La6&[La@B24]+/0 (3/4) clusters, while the 1D La10B32 (5), 2D La3B10 (6), and 3D LaB6 (7) crystals exhibit mainly electrostatic interactions between the trivalent La centers and cubic B24 frameworks, with weak but discernible coordination contributions from La (5d) ← B (2p) back-donations. The IR and Raman spectra of La6&[La@B24]+/0 (3/4) and band structures of La10B32 (5) and La3B10 (6) are computationally simulated to facilitate their future characterizations.