Infrared bands of neutral gas-phase carbon clusters in a broad spectral range.

The identification of species in the interstellar medium requires precise and molecule-specific spectroscopic information in the laboratory framework, in broad spectral ranges and under conditions relevant to interstellar environments. In this work, we measure the gas-phase infrared spectra of neutral carbon clusters, CN (N = 6-11), in a molecular beam. The CN distribution is formed by photofragmentation of C60 molecules, concurrently showing a top-down formation mechanism. A broad spectral range in the infrared between 500-3200 cm-1 (20-3.125 µm) is investigated. We observe strong bands between 5 and 6 µm, in conjunction with novel features in the 3 µm region. Density functional theory calculations reveal that these short wavelength modes correspond to combination bands with significant infrared intensity. Moreover, we identify the N ≤ 10 clusters as linear, while C11 adopts a ring configuration, placing the linear-to-ring transition at N = 11 under our molecular beam conditions. The linearity of C10 is discussed based on the formation pathway from larger clusters in energetic conditions. Given the vast and very precise infrared information already been released from the James Webb Space Telescope mission, this infrared spectroscopic data set in conjunction with information on formation mechanisms is of major relevance for identifying neutral carbon clusters in astronomical environments.

The infrared absorption spectrum of phenylacetylene and its deuterated isotopologue in the mid- to far-IR.

Anharmonicity strongly influences the absorption and emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules. Here, IR-UV ion-dip spectroscopy experiments together with detailed anharmonic computations reveal the presence of fundamental, overtone, as well as 2- and 3-quanta combination band transitions in the far- and mid-infrared absorption spectra of phenylacetylene and its singly deuterated isotopologue. Strong absorption features in the 400-900 cm-1 range originate from CH(D) in-plane and out-of-plane wags and bends, as well as bending motions including the C≡C and CH bonds of the acetylene substituent and the aromatic ring. For phenylacetylene, every absorption feature is assigned either directly or indirectly to a single or multiple vibrational mode(s). The measured spectrum is dense, broad, and structureless in many regions but well characterized by computations. Upon deuteration, large isotopic shifts are observed. At frequencies above 1500 cm-1 for d1-phenylacetylene, a one-to-one match is seen when comparing computations and experiments with all features assigned to combination bands and overtones. The C≡C stretch observed in phenylacetylene is not observed in d1-phenylacetylene due to a computed 40-fold drop in intensity. Overall, a careful treatment of anharmonicity that includes 2- and 3-quanta modes is found to be crucial to understand the rich details of the infrared spectrum of phenylacetylene. Based on these results, it can be expected that such an all-inclusive anharmonic treatment will also be key for unraveling the infrared spectra of PAHs in general.

Fragmentation channels of non-fullerene cationic carbon clusters.

The unimolecular fragmentation channels of highly excited small cationic carbon clusters have been measured with a time-of-flight mass spectrometer after photofragmentation. The dominant channel is loss of the neutral trimer, for all CN+N = 10-27 clusters except for N = 11, 12 which decay by monomer emission, and C25+ which shows competing loss of C2 and C3. The results permit to quantify the role of the rotational entropy in the competition between monomer and trimer decays with the help of energies calculated with density functional theory.

Wetting of a Hydrophobic Surface: Far-IR Action Spectroscopy and Dynamics of Microhydrated Naphthalene.

The interaction of water and polycyclic aromatic hydrocarbons is of fundamental importance in areas as diverse as materials science and atmospheric and interstellar chemistry. The interplay between hydrogen bonding and dipole-π interactions results in subtle dynamics that are challenging to describe from first principles. Here, we employ far-IR action vibrational spectroscopy with the infrared free-electron laser FELIX to investigate naphthalene with one to three water molecules. We observe diffuse bands associated with intermolecular vibrational modes that serve as direct probes of the loose binding of water to the naphthalene surface. These signatures are poorly reproduced by static DFT or Møller-Plesset computations. Instead, a rationalization is achieved through Born-Oppenheimer Molecular Dynamics simulations, revealing the active mobility of water over the surface, even at low temperatures. Therefore, our work provides direct insights into the wetting interactions associated with shallow potential energy surfaces while simultaneously demonstrating a solid experimental-computational framework for their investigation.

Best management practices for minimizing undesired effects of thermal remediation and soil washing on soil properties. A review.

The use of remediated soils as end-of-life materials raises some challenges including policy and regulation, permits and specifications, technological limitations, knowledge and information, costs, as well as quality and performance associated with using them. Therefore, a set of procedures must be followed to preserve the quality and fundamental properties of soil during a remediation process. This study presented a comprehensive review regarding the fundamental impacts of thermal desorption (TD) and soil washing (SW) on soil characteristics. The effects of main operating parameters of TD and SW on the physical, chemical, and biological properties of soil were systematically reviewed. In TD, temperature has a more remarkable effect on physic-chemical and biological characteristics of soil than heating time. Therefore, decrease in temperature within a suitable range prevents unreversible changes on soil properties. In SW, more attention should be paid to extraction process of contaminants from soil particles. Using the right dosage and type of chelating agents, surfactants, solvents, and other additives can help to avoid problems with recovery or treatment using conventional methods. In addition, this review introduced a framework for implementing sustainable remediation approaches based on a holistic approach to best management practices (BMPs), which, besides reducing the risks associated with different pollutants, might provide new horizons for decreasing the unfavourable impacts of TD and SW on soil.

A multidisciplinary approach to estimating wolf population size for long-term conservation.

The wolf (Canis lupus) is among the most controversial of wildlife species. Abundance estimates are required to inform public debate and policy decisions, but obtaining them at biologically relevant scales is challenging. We developed a system for comprehensive population estimation across the Italian alpine region (100,000 km2 ), involving 1513 trained operators representing 160 institutions. This extensive network allowed for coordinated genetic sample collection and landscape-level spatial capture-recapture analyses that transcended administrative boundaries to produce the first estimates of key parameters for wolf population status assessment. Wolf abundance was estimated at 952 individuals (95% credible interval 816-1120) and 135 reproductive units (i.e., packs) (95% credible interval 112-165). We also estimated that mature individuals accounted for 33-45% of the entire population. The monitoring effort was spatially estimated thereby overcoming an important limitation of citizen science data. This is an important approach for promoting wolf-human coexistence based on wolf abundance monitoring and an endorsement of large-scale harmonized conservation practices.

Una estrategia multidisciplinaria para la estimación del tamaño poblacional de los lobos para la conservación a largo plazo Resumen El lobo (Canis lupus) está entre las especies de fauna más controversiales. Se requieren estimaciones de abundancia para informar al debate público y las decisiones políticas, pero es un reto obtenerlos en escalas con relevancia biológica. Desarrollamos un sistema para la estimación completa de la población en la región alpina de Italia (100,000 km2 ), con la participación de 1,513 operadores entrenados que representan a 160 instituciones. Esta red extensa permitió una colecta coordinada de muestras genéticas y análisis de captura-recaptura espacial que trascendieron las fronteras administrativas para así producir las primeras estimaciones de los parámetros clave para la evaluación del estado de la población de los lobos. Se estimó la abundancia en 952 individuos (95% intervalo de confianza 816-1120) y 135 unidades reproductivas (es decir, manadas) (95% intervalo de confianza 112-165). También estimamos que los individuos maduros representaban el 33-45% de toda la población. El esfuerzo de monitoreo se estimó espacialmente, por lo que sobrepasó una limitación importante de la ciencia ciudadana. Esta estrategia es importante para promover la coexistencia entre lobos y humanos con base en el monitoreo de la abundancia y el apoyo a las prácticas armonizadas de conservación a gran escala.

Radiative cooling in silver and palladium doped gold clusters.

The emission of photons from a thermally populated electronic excited state, via the process of recurrent fluorescence, has been recognized as a prominent cooling channel in hot molecules and small metal clusters. For the latter case, however, only monometallic species have been investigated to date. An active radiative cooling channel has a stabilizing effect and can favor the size and composition specific production of selected clusters. In this work, the influence of silver and palladium doping on the radiative cooling of gold cluster cations is studied. The quenching of metastable fragmentation due to radiation of laser-excited Aun+, AgAun-1+ and PdAun-1+ (n = 11-15) clusters is investigated in a single-pass molecular beam setup. The observed high radiation rates, with values in the range from 103 to 105 s-1, are consistent with recurrent fluorescence. The rates present a pronounced odd-even staggering with higher values for the clusters with closed-shell electronic configurations. While substitution of Au with Ag does not alter the odd-even pattern with cluster size, replacing Au with Pd shifts the pattern by one atom. The experimental observations are discussed in terms of the dissociation energy of the clusters, which sets their effective temperature during photon emission, and the low-lying electronic excited states involved in the photon emission process. Linear-response time-dependent density functional theory calculations on selected species are used to illustrate the significant effect of the electronic structure on the radiation rates. For n = 14, substitution of Au with Ag lowers the energy of the lowest-energy transition in the cluster, which in addition has a higher oscillator strength, favoring radiative cooling. The opposite effect is seen in Pd doped clusters. Based on this analysis, conclusions can be drawn about the significance of radiative cooling in laser-excited alloy clusters, with a concomitant fast stabilization at high internal energy conditions.

Influence of oxidation on the magnetism of small Co oxide clusters probed by Stern-Gerlach deflection.

We report on the magnetic properties of small neutral suboxide ConOm (n = 5-18 and m = 0-10, m ≤ n) clusters produced by laser vaporisation and gas aggregation. Their magnetism is probed experimentally by means of Stern-Gerlach magnetic deflection. The results imply that the cobalt atoms couple ferromagnetically not only in pure Con clusters, as known from previous investigations, but also in their oxidized counterparts. It was found that the magnetic moment per cobalt atom is mostly enhanced in the oxide clusters with respect to the pure cobalt clusters and generally increases with the oxygen content in the studied composition range. The spin magnetism of selected clusters is also investigated by density functional theory (DFT) calculations. The computations allow to attribute the effect of oxidation on the magnetic response of the ConOm clusters to electron transfer from the cobalt 3d and 4s valence orbitals to oxygen. The cobalt 3d levels preferentially donate electrons of minority spin, but both spin orientations are involved in the transfer of cobalt 4s electrons.

Spectroscopic evidence of a Xe-Xe bond in the linear Xe2Au+Xe ion.

The closed-shell nature of Xe atoms precludes the formation of Xe-Xe bonds other than based on van der Waals interactions. Here, we present experimental evidence showing that the complexation of Xe atoms to a Au+ ion leads to stabilization of a Xe-Xe interaction going beyond purely dispersive. Infrared spectroscopy is used to identify the geometry of AuXe3+ as a linear structure in which two Xe atoms form a direct bond, instead of an expected geometry in which three Xe atoms coordinate directly with a central Au+ ion. Density functional theory and coupled-cluster calculations show that this bond possesses an enhanced orbital mixture, in comparison to that in the isolated Xe2 dimer. The calculations are validated by observed vibrational modes at 134 and 163 cm-1 for AuXe3+, and a AuXe2+-Xe bond energy of 0.04 ± 0.01 eV estimated from the temperature-dependent formation.

The spin magnetic order of Con+ (n ≤ 5) clusters.

The magnetism of transition metal clusters has been for decades a complicated puzzle, with experimental results disagreeing with calculations performed within the density functional theory formalism. In this work, we provide a key to this puzzle by investigating the lowest-energy spin states of cobalt cluster, Con+ (n ≤ 5), using CASSCF/NEVPT2 calculations with very large active spaces. The geometries as well as the spin configurations adopted by the clusters in their ground-state are known from experiments, making Con+ clusters an ideal model system for theoretical investigation. Here, using the experimentally known geometries determined by far-infrared spectroscopy as inputs, we calculated the lowest-energy spin configurations of the clusters, revealing that the CASSCF/NEVPT2 formalism correctly predicts the preferred electronic configuration of the clusters known experimentally. This is in contrast to the widely used density functional theory, with results that depend on the selected exchange-correlation functional. The reasons for the failure of density functional theory, in opposition to CASSCF/NEVPT2, are discussed, providing a solid framework for investigating other transition metal and transition metal oxide clusters.

Bonding Nature between Noble Gases and Small Gold Clusters.

Noble gases are usually seen as utterly inert, likewise gold, which is typically conceived as the noblest of all metals. While one may expect that noble gases bind to gold via dispersion interactions only, strong bonds can be formed between noble gas atoms and small gold clusters. We combine mass spectrometry, infrared spectroscopy, and density functional theory calculations to address the bonding nature between Aun+ (n ≤ 4) clusters and Ar, Kr, and Xe. We unambiguously determine the geometries and quantitatively uncover the bonding nature in AunNgm+ (Ng = Ar, Kr, Xe) complexes. Each Au cluster can form covalent bonds with atop bound noble gas atoms, with strengths that increase with the noble gas atomic radius. This is demonstrated by calculated adsorption energies, Bader electron charges, and analysis of the electron density. The covalent bonding character, however, is limited to the atop-coordinated Ng atoms.

The wavelength-dependent non-linear absorption and refraction of Au25 and Au38 monolayer-protected clusters.

In the past decade, the structural and electronic properties of monolayer-protected metal clusters, which can be produced size-selected in macroscopic amounts, have received a lot of attention. Their great potential for optical applications has been identified. In the high intensity regime, monolayer-protected metal clusters show pronounced nonlinear absorption and refraction. Naturally, these phenomena are wavelength-dependent, however, such dependence is largely unexplored. Here, we quantify the wavelength-dependent non-linear optical absorption and refraction cross sections of atomically precise Au25(DDT)18 and Au38(DDT)24 clusters, using the z-scan technique in combination with a tunable nanosecond laser source. Qualitatively different non-linear optical phenomena were found to take place at different excitation wavelengths (two-photon and excited-state absorption, intensity saturation and non-linear refraction). Both clusters have high nonlinear absorption cross sections at 532 nm, and present a (local) maximum at 640 nm, together with a maximum in the absorption saturation. The nonlinear refraction is always negative for Au25(DDT)18, while it changes sign for Au38(DDT)24. Depending on the wavelength, the underlying mechanism of the nonlinear absorption effects is two-photon absorption or excited state absorption. The obtained very high nonlinear cross sections, on the order of 107-109 GM, demonstrate the great potential of those clusters as nonlinear absorption or refraction materials in optical applications.

The size-dependent influence of palladium doping on the structures of cationic gold clusters.

The physicochemical properties of small metal clusters strongly depend on their precise geometry. Determining such geometries, however, is challenging, particularly for clusters formed by multiple elements. In this work, we combine infrared multiple photon dissociation spectroscopy and density functional theory calculations to investigate the lowest-energy structures of Pd doped gold clusters, PdAu n-1 + (n ≤ 10). The high-quality experimental spectra allow for an unambiguous determination of the structures adopted by the clusters. Our results show that the Pd-Au interaction is so large that the structures of PdAu n-1 + and Au n + are very different. Pd doping induces a 2D to 3D transition at much smaller cluster sizes than for pure Au n + clusters. PdAu n-1 + clusters are three-dimensional from n = 4, whereas for Au n + this transition only takes place at n = 7. Despite the strong Au-Pd interaction, the Au n-1 + cluster geometries remain recognizable in PdAu n-1 + up to n = 7. This is particularly clear for PdAu6 +. In PdAu8 + and PdAu9 +, Pd triggers major rearrangements of the Au clusters, which adopt pyramidal shapes. For PdAu4 + we find a geometry that was not considered in previous studies, and the geometry found for PdAu8 + does not correspond to the lowest-energy structure predicted by DFT, suggesting kinetic trapping during formation. This work demonstrates that even with the continuous improvement of computational methods, unambiguous assignment of cluster geometries still requires a synergistic approach, combining experiment and computational modelling.

Water Splitting by C60 -Supported Vanadium Single Atoms.

Water splitting is an important source of hydrogen, a promising future carrier for clean and renewable energy. A detailed understanding of the mechanisms of water splitting, catalyzed by supported metal atoms or nanoparticles, is essential to improve the design of efficient catalysts. Here, we report an infrared spectroscopic study of such a water splitting process, assisted by a C60 supported vanadium atom, C60 V+ +H2 O→C60 VO+ +H2 . We probe both the entrance channel complex C60 V+ (H2 O) and the end product C60 VO+ , and observe the formation of H2 as a result from resonant infrared absorption. Density functional theory calculations exploring the detailed reaction pathway reveal that a quintet-to-triplet spin crossing facilitates the water splitting reaction by C60 -supported V+ , whereas this reaction is kinetically hindered on the isolated V+ ion by a high energy barrier. The C60 support has an important role in lowering the reaction barrier with more than 70 kJ mol-1 due to a large orbital overlap of one water hydrogen atom with one carbon atom of the C60 support. This fundamental insight in the water splitting reaction by a C60 -supported single vanadium atom showcases the importance of supports in single atom catalysts by modifying the reaction potential energy surface.

An octacoordinated Nb atom in the NbAl8H8+ cluster.

The NbAl8H8+ cluster was formed in a molecular beam and characterized by mass spectrometry and infrared spectroscopy. Density functional theory calculations show the lowest-energy isomer is a high symmetry singlet with the Nb atom placed at the center of a distorted hexagonal Al ring and coordinated by two AlH moieties, therefore exhibiting octacoordination. The unprecedented high-symmetric geometry is attributed to the 20 valence electrons; the central Nb atom adheres to the 18-electron rule and two additional delocalized electrons stabilize the hexagonal ring.

Computing gold cluster energies with density functional theory: the importance of correlation.

Energies calculated with density functional theory depend critically on the choice of the exchange-correlation functional. In this work, we use measured dissociation energies of Aun+ (n = 5-17) clusters as benchmark data to test two very different functionals for calculating total energies in these clusters; the simpler (and fast) PBE and the evolved (and expensive) B2PLYP double-hybrid functionals. PBE consistently gives poor agreement with the experimental results. In contrast, the B2PLYP functional, which implicitly includes electron correlation by performing a perturbative second-order correction, significantly improves the agreement of the calculations, at the cost of much more demanding computations. The better performance of the double-hybrid functional is ascribed to the longer range of the interatomic potential.

Argon Adsorption on Cationic Gold Clusters Aun+ (n ≤ 20).

The interaction of Aun+ (n ≤ 20) clusters with Ar is investigated by combining mass spectrometric experiments and density functional theory calculations. We show that the inert Ar atom forms relatively strong bonds with Aun+. The strength of the bond strongly varies with the cluster size and is governed by a fine interplay between geometry and electronic structure. The chemical bond between Aun+ and Ar involves electron transfer from Ar to Au, and a stronger interaction is found when the Au adsorption site has a higher positive partial charge, which depends on the cluster geometry. Au15+ is a peculiar cluster size, which stands out for its much stronger interaction with Ar than its neighbors, signaled by a higher abundance in mass spectra and a larger Ar adsorption energy. This is shown to be a consequence of a low-coordinated Au adsorption site in Au15+, which possesses a large positive partial charge.

Doping Platinum with Germanium: An Effective Way to Mitigate the CO Poisoning.

The vulnerability towards CO poisoning is a major drawback affecting the efficiency and long-term performance of platinum catalysts in fuel cells. In the present work, by a combination of density functional theory calculations and mass spectrometry experiments, we test and explain the promotional effect of Ge on Pt catalysts with higher resistance to deactivation via CO poisoning. A thorough exploration of the configurational space of gas-phase Ptn + and GePtn-1 + (n=5-9) clusters using global minima search techniques and the subsequent electronic structure analysis reveals that germanium doping reduces the binding strength between Pt and CO by hindering the 2π-back-donation. Importantly, the clusters remain catalytically active towards H2 dissociation. The ability of Ge to weaken the Pt-CO interaction was confirmed by mass spectrometry experiments. Ge can be a promising alloying agent to tune the selectivity and improve the durability of Pt particles, thus opening the way to novel catalytic alternatives for fuel cells.

Argon tagging of doubly transition metal doped aluminum clusters: The importance of electronic shielding.

The interaction of argon with doubly transition metal doped aluminum clusters, AlnTM2 + (n = 1-18, TM = V, Nb, Co, Rh), is studied experimentally in the gas phase via mass spectrometry. Density functional theory calculations on selected sizes are used to understand the argon affinity of the clusters, which differ depending on the transition metal dopant. The analysis is focused on two pairs of consecutive sizes: Al6,7V2 + and Al4,5Rh2 +, the largest of each pair showing a low affinity toward Ar. Another remarkable observation is a pronounced drop in reactivity at n = 14, independent of the dopant element. Analysis of the cluster orbitals shows that this feature is not a consequence of cage formation but is electronic in nature. The mass spectra demonstrate a high similarity between the size-dependent reactivity of the clusters with Ar and H2. Orbital interactions provide an intuitive link between the two and further establish the importance of precursor states in the reactions of the clusters with hydrogen.