RESUMEN
The identification of the non-noble metal constituted TaO cluster as a potential analogue to the noble metal Au is significant for the development of tailored materials. It leverages the superatom concept to engineer properties with precision. However, the impact of incrementally integrating TaO units on the electronic configurations and properties within larger TaO-based clusters remains to be elucidated. By employing the density functional theory calculations, the global minima and low-lying isomers of the TanOn (n = 2-5) clusters were determined, and their structural evolution was disclosed. In the cluster series, Ta5O5 was found to possess the highest electron affinity (EA) with a value of 2.14 eV, based on which a dual external field (DEF) strategy was applied to regulate the electronic property of the cluster. Initially, the electron-withdrawing CO ligand was affixed to Ta5O5, followed by the application of an oriented external electric field (OEEF). The CO ligation was found to be able to enhance the Ta5O5 cluster's electron capture capability by adjusting its electron energy levels, with the EA of Ta5O5(CO)4 peaking at 2.58 eV. Subsequently, the introduction of OEEF further elevated the EA of the CO-ligated cluster. Notably, OEEF, when applied along the +x axis, was observed to sharply increase the EA to 3.26 eV, meeting the criteria for superhalogens. The enhancement of EA in response to OEEF intensity can be quantified as a functional relationship. This finding highlights the advantage of OEEF over conventional methods, demonstrating its capacity for precise and continuous modulation of cluster EAs. Consequently, this research has adeptly transformed tantalum oxide clusters into superhalogen structures, underscoring the effectiveness of the DEF strategy in augmenting cluster EAs and its promise as a viable tool for the creation of superhalogens.
RESUMEN
Nitrogen fixation is confronted with great challenges in the field of chemistry. Herein, we report that single metal carbides PtCn- and PtCnN2- (n = 4-6) are indispensable intermediates in the process of nitrogen fixation by mass spectrometry coupled with anionic photoelectron spectroscopy, quantum chemical calculations, and simulated density-of-state spectra. The most stable isomers of these cluster anions are characterized to have linear chain structures. The fixation and activation of dinitrogen are facilitated by the charge transfer from Pt and Cn to N2. The significance of π back-donation of the 5d orbital of the Pt atom to the antibonding π orbits of N2 for dinitrogen fixation and activation is discussed in detail. This study not only provides a theoretical basis at the molecular level for the activation of dinitrogen by mononuclear metal carbide clusters but also provides a new paradigm for dinitrogen fixation.
RESUMEN
Spectroscopic characterization of ketenylidene complexes is of essential importance for understanding the structure-reactivity relationships of the catalytic sites. Here, we report a size-specific photoelectron velocity map imaging spectroscopic study of the reactions of carbon monoxide with nickel carbide. Quantum chemical calculations have been conducted to search for the energetically favorable isomers and to recognize the experimental spectra. The target products with the chemical formula of NiC(CO)n- (n = 3-5) are characterized to have an intriguing ketenylidene CCO unit. The evolution from NiC(CO)3- to NiC(CO)4- involves the breaking and formation of the Ni-C bond and the coordination conversion between the terminal and bridging carbonyls. Experimental and theoretical analyses reveal an efficient C-C bond formation process within the reactions of carbon monoxide and laser-vaporized nickel carbide. This work highlights the pivotal roles played by metal carbides in the C-C bond formation and also proposes new ideas for the design and chemical control of a broad class of complexes with unique physical and chemical properties.
RESUMEN
The structural and bonding properties of the Pt2C2n - (n = 1-3) complexes have been investigated by mass-selected photoelectron velocity-map imaging spectroscopy with quantum chemical calculations. The adiabatic detachment energies and vertical detachment energies of Pt2C2n - have been obtained from the measured photoelectron imaging spectra. Theoretical results indicate that the lowest-energy isomers of Pt2C2n - (n = 1-3) possess linear chain-shaped configurations. The binding motif in the most stable isomer of Pt2C2 - has a linear cumulenic structure with a Pt=C=C=Pt configuration, and the structural characteristic persists up to all the lowest-energy isomers of the Pt2C4 - and Pt2C6 - anions. The chemical bonding analyses indicate that the Pt2C2n - (n = 1-3) complexes have multicenter two-electron characteristics.
RESUMEN
Traditional electron counting rules, like the Jellium model, have long been successfully utilized in designing superhalogens by modifying clusters to have one electron less than a filled electronic shell. However, this shell-filling approach, which involves altering the intrinsic properties of the clusters, can be complex and challenging to control, especially in experiments. In this letter, we theoretically establish that the oriented external electric field (OEEF) can substantially enhance the electron affinity (EA) of diverse aluminum-based metal clusters with varying valence electron configurations, leading to the creation of superhalogen species without altering their shell arrangements. This OEEF approach offers a noninvasive alternative to traditional superatom design strategies, as it does not disrupt the clusters' geometrical structures and superatomic states. These findings contribute a vital piece to the puzzle of constructing superalkalis and superhalogens, extending beyond conventional shell-filling strategies and potentially expanding the range of applications for functional clusters.
RESUMEN
Nitrogen activation is a significant but difficult project in the chemical area. Photoelectron spectroscopy (PES) and calculated results are used to investigate the reaction mechanism of the heteronuclear bimetallic cluster FeV- toward N2 activation. The results clearly show that N2 can be fully activated by FeV- at room temperature, forming the FeV(µ2-N)2- complex with the totally ruptured N≡N bond. Electronic structure analysis reveals that the activation of N2 by FeV- is achieved by the electron transfer of bimetallic atoms and electron back-donation to the metal core, which demonstrates that heteronuclear bimetallic anionic clusters are very important to nitrogen activation. This study provides important information for the rational design of synthetic ammonia catalysts.
RESUMEN
Herein, the configurations and intrinsic electronic properties of heteronuclear transition metal dioxide carbonyl anions Ni2TiO2(CO) n - (n = 2-4) in the gas phase were investigated using mass spectrometry coupled anionic photoelectron spectroscopy, ab initio calculations, and simulated density-of-state (DOS) spectra. The results clearly show that the binding of electrons is enhanced by the addition of CO. The ground state structures of Ni2TiO2(CO) n - (n = 2-4) are characterized to show that three transition metal atoms (one Ti atom and two Ni atoms) forming a quasi-line is favored. The interaction between Ni and C becomes weaker as the cluster size increases. The natural electron configuration shows that the extra electron is enriched on O atoms attached to Ti, and there is strong interaction between Ti and O atoms. This work gives significant insight into the configuration and electronic structures of nickel-titanium dioxide carbonyl anions, which has potential application in adsorption of carbon monoxide on the surfaces/interfaces of alloys.
RESUMEN
Electron adsorption ionization ion mobility spectrometry can be used to detect halogen-containing volatile organic compounds with high sensitivity. However, this traditional electron attachment detection method cannot distinguish between volatile organic compounds containing the same halogen. For different organic compounds containing the same halogen, the product ions formed by the dissociation electron attachment process are the same. In this article, we propose a novel negative corona discharge ion mobility spectrometry method to distinguish between and detect halogenated alkanes containing the same halogen according to the different electron attachment rates and reaction kinetic parameters of the different halogenated alkanes. Although these halogenated alkanes, which contain the same halogen, produce the same type of ions through the electron attachment process, their electron attachment rates are different from each other. In this work, the kinetic information is used as the fingerprint information for the tested samples to distinguish different halogenated alkanes. Five halogenated alkanes were successfully detected using this method. The results show that the method based on the electron attachment rate constant is feasible for the determination of halogenated alkanes containing the same halogen.