Anion Photoelectron Spectroscopy Research Articles

Probing the geometric and electronic structure of Rhodium Oxide Clusters (RhO)n− (n = 2-4) by anion photoelectron spectroscopy and theoretical calculations

Probing the geometric and electronic structure of Rhodium Oxide Clusters (RhO)n− (n = 2-4) by anion photoelectron spectroscopy and theoretical calculations

Hexagonal Bipyramidal Mn3Ge5 Cluster and Its One-Dimensional Ferrimagnetic Sandwich Nanowire: Mn3Ge3 Rings as Structural Motifs.

Bipyramidal structures featuring planar rings serve as potential building blocks for one-dimensional (1D) nanostructures. Pure Ge atoms typically prefer to form three-dimensional rather than planar structures. Although a few-metal-doped bipyramids with pure Ge planar rings are predicted for constructing Ge-based 1D nanostructures, there is limited knowledge about those with both Ge and doped atoms on the same planar rings. Here, we report a hexagonal bipyramidal Mn3Ge5 cluster containing a Mn3Ge3 six-membered ring with the potential to construct a 1D germanium-based nanostructure. We investigated the structures and properties of Mn3Ge5-/0 using anion photoelectron spectroscopy and theoretical calculations. Mn3Ge5- has a C3v symmetric distorted hexagonal bipyramidal structure, while Mn3Ge5 has a C2v symmetric hexagonal bipyramidal structure. Chemical bonding analyses show that Mn3Ge5- could be considered as a [Mn3]V[Ge5]6- complex. First-principles calculations indicate that Mn3Ge5 may be used to construct a 1D ferrimagnetic [Mn3Ge5]∞ nanostructure.

Structural and bonding characteristics in Au2Ge9ˉ and Au2Ge10ˉ clusters: insights from photoelectron spectroscopy and theoretical calculations

Germanium-based materials exhibit promising properties for applications in electronics, sensing, and catalysis. Gold-germanium clusters are of particular interest due to their potential for enhanced stability and tailored electronic properties. This study investigates the structures, bonding, and electronic properties of Au2Ge9ˉ and Au2Ge10ˉ clusters using anion photoelectron spectroscopy and theoretical calculations. The clusters were generated using laser vaporization and studied using anion photoelectron spectroscopy. Theoretical calculations employed density functional theory and coupled-cluster methods. Au2Ge9ˉ and Au2Ge10ˉ clusters exhibit weak aurophilic interactions between the two gold atoms. The gold atoms mimic the electronic and structural properties of germanium atoms, acting as surrogates within the cluster framework. Understanding the role of gold in these germanium clusters provides insights for designing novel materials with tailored properties for applications in catalysis, electronics, and other fields.

Spectroscopic Quantification of the Inverted Singlet-Triplet Gap in Pentaazaphenalene.

We report the direct and accurate spectroscopic quantification of the inverted singlet-triplet gap in 1,3,4,6,9b-pentaazaphenalene. This measurement is achieved by directly probing the lowest singlet and triplet states via high-resolution cryogenic anion photoelectron spectroscopy. The assignment of the first excited singlet state is confirmed by visible absorption spectroscopy in an argon matrix at 20 K. Our measurements yield an inverted singlet-triplet gap with ΔEST= -0.047(7) eV. The accurate quantification of the singlet-triplet gap presented here allows for direct evaluation of various computational electronic structure methods and highlights the critical importance of the proper description of the double excitation character of these electronic states. Overall, this study validates the idea that despite Hund's multiplicity rule, useful organic chromophores can have inherently inverted singlet-triplet gaps.

Structural evolution and bonding properties of Nb1-2Gen-/0 (n = 3-7) clusters: Anion photoelectron spectroscopy and theoretical calculations.

This study presents a collaborative experimental and theoretical investigation into the structures and electronic properties of niobium-doped germanium clusters. Anion photoelectron spectra for Nb1-2Gen- (n = 3-7) clusters were acquired using 266nm photon energies, enabling the determination of adiabatic detachment energies and vertical detachment energies. In conjunction with these experimental measurements, density functional theory (DFT) calculations were conducted to validate the experimentally obtained electron detachment energies and elucidate the geometric and electronic structures of each anionic cluster. The agreement between DFT calculations and experimental data establishes a solid foundation for assessing the structural evolution and electronic properties of niobium-doped germanium clusters. It is noted that both neutral and anionic clusters exhibit predominantly similar overall structural characteristics, with the exception of Nb2Ge6- and Nb2Ge6. Furthermore, this investigation emphasizes the exceptional chemical stability of the D3d symmetric chair-shaped structure in Nb2Ge6-, providing insights into its bonding characteristics.

Gas-Phase Structures of [Au21(SR)14]- and [Au17(SR)10]- with Eight Electrons: Can They Support an Icosahedral Au13 Core?

A prototypical thiolate (RS)-protected gold cluster [Au25(SR)18]- has high stability due to specific geometric and electronic structures: an icosahedral (Ih) Au13 core with a closed electronic shell containing eight electrons is completely protected by six units of Au2(SR)3. Nevertheless, collisional excitation of [Au25(SR)18]- in a vacuum induces the sequential release of Au4(SR)4 to form [Au21(SR)14]- and [Au17(SR)10]- both containing eight electrons. To answer a naive question of whether these fragments bear an Ih Au13(8e) core, the geometrical structures of [Au21(SC3H7)14]- and [Au17(SC3H7)10]- in the gas phase were examined by the combination of anion photoelectron spectroscopy and density functional theory (DFT) calculation of simplified models of [Au21(SCH3)14]- and [Au17(SCH3)10]-. We concluded that [Au21(SC3H7)14]- retains a slightly distorted Ih Au13(8e) core, while [Au17(SC3H7)10]- has an amorphous Au13 core composed of triangular Au3, tetrahedral Au4, and prolate Au7 units. DFT calculations on putative species [Au19(SCH3)12]- and [Au18(SCH3)11]- suggested that the Ih Au13(8e) core undergoes dramatic structural deformation due to mechanical stress from μ2 ligation of only one RS.

Unveiling the structural and bonding properties of AuSi2- and AuSi3- clusters: A comprehensive analysis of anion photoelectron spectroscopy and abinitio calculations.

Silicon clusters infused with transition metals, notably gold, exhibit distinct characteristics crucial for advancing microelectronics, catalysts, and energy storage technologies. This investigation delves into the structural and bonding attributes of gold-infused silicon clusters, specifically AuSi2- and AuSi3-. Utilizing anion photoelectron spectroscopy and abinitio computations, we explored the most stable isomers of these clusters. The analysis incorporated Natural Population Analysis, electron localization function, molecular orbital diagrams, adaptive natural density partitioning, and Wiberg bond index for a comprehensive bond assessment. Our discoveries reveal that cyclic configurations with the Au atom atop the Si-Si linkage within the fundamental Si2 and Si3 clusters offer the most energetically favorable structures for AuSi2- and AuSi3- anions, alongside their neutral counterparts. These anions exhibit notable highest occupied molecular orbital-lowest unoccupied molecular orbital gaps and significant σ and π bonding patterns, contributing to their chemical stability. Furthermore, AuSi2- demonstrates π aromaticity, while AuSi3- showcases a distinctive blend of σ antiaromaticity and π aromaticity, crucial for their structural robustness. These revelations expand our comprehension of gold-infused silicon clusters, laying a theoretical groundwork for their potential applications in high-performance solar cells and advanced functional materials.

Anion Photoelectron Spectroscopy and Quantum Chemistry Calculations of Gas-Phase TaSi17̅ and TaSi18̅ Clusters: Structural Determination, Bonding Characteristics, and Multiplicity of Structural Forms.

This study explores the structures and chemical bonding properties of TaSi17̅ and TaSi18̅ clusters by employing anion photoelectron spectroscopy and theoretical computations. Utilizing CALYPSO and ABCluster programs for initial structure prediction, B3LYP hybrid functional for optimization, and CCSD(T)/def2-TZVPPD level for energy calculations, the research identifies the most stable isomers of these clusters. Key findings include the identification of two coexisting low-energy isomers for TaSi17̅, exhibiting Ta-endohedral fullerene-like cage structures, and the lowest-energy structures of TaSi17̅ and TaSi18̅ anions can be considered as derived from the TaSi16̅ superatom cluster. The study enhances the understanding of group 14 element chemistry and guides the design of novel inorganic metallic compounds, potentially impacting materials science.

The valence electron affinity of uracil determined by anion cluster photoelectron spectroscopy.

The unoccupied π* orbitals of the nucleobases are considered to play important roles in low-energy electron attachment to DNA, inducing damage. While the lowest anionic valence state is vertically unbound in all neutral nucleobases, it remains unclear even for the simplest nucleobase, uracil (U), whether its valence anion (U-) is adiabatically bound, which has important implications on the efficacy of damage processes. Using anion photoelectron spectroscopy, we demonstrate that the valence electron affinity (EAV) of U can be accurately measured within weakly solvating clusters, U-(Ar)n and U-(N2)n. Through extrapolation to the isolated U limit, we show that EAV = -2 ± 18 meV. We discuss these findings in the context of electron attachment to U and its reorganization energy, and more generally establish guidance for the determination of molecular electron affinities from the photoelectron spectroscopy of anion clusters.

Structural and bonding analysis of PtO2− anion and neutral clusters

This study investigates the structures and bonding properties of gas-phase PtO2ˉ anion and PtO2 neutral using anion photoelectron spectroscopy and theoretical calculations. Notably, both species adopt a D∞h symmetric linear O−Pt−O structure, with PtO2 neutral featuring notably shorter Pt–O bond lengths. Charge transfer from the central Pt atom to the terminal O2 motifs is evident in both clusters, as indicated by Natural Population Analysis (NPA). Chemical bonding analysis reveals σ and π double bonding patterns in PtO2ˉ anion, while PtO2 neutral demonstrates σ and π antiaromaticity. This research enhances our understanding of platinum oxide clusters and their potential in developing co-catalysts for efficient solar-driven water splitting.

The unusual quadruple bonding of nitrogen in ThN

Nitrogen has five valence electrons and can form a maximum of three shared electron-pair bonds to complete its octet, which suggests that its maximum bond order is three. With a joint anion photoelectron spectroscopy and quantum chemistry investigation, we report herein that nitrogen presents a quadruple bonding interaction with thorium in ThN. The quadruple Th≣N bond consists of two electron-sharing Th-N π bonds formed between the Th-6dxz/6dyz and N 2px/2py orbitals, one dative Th←N σ bond and one weak Th←N σ bonding interaction formed between Th-6dz2 and N 2s/2pz orbitals. The ThC molecule has also been investigated and proven to have a similar bonding pattern as ThN. Nonetheless, due to one singly occupied σ-bond, ThC is assigned a bond order of 3.5. Moreover, ThC has a longer bond length as well as a lower vibrational frequency in comparison with ThN.

Reconsidering the Structures of C2 Al4 - and C2 Al5.

The study of C2 Al4 -/0 and C2 Al5 -/0 was conducted using anion photoelectron spectroscopy and quantum chemical computations. The present findings reveal that C2 Al4 - has a boat-like structure, with a single C2 unit surrounded by four aluminum atoms. In contrast, the neutral C2 Al4 species adopts a D2h planar structure with two planar tetracoordinate carbon (ptC) units, consistent with previous reports. Furthermore, the global minimum isomer of C2 Al5 - adopts a D3h symmetry, where the C2 unit interacts with five aluminum atoms. It was also found that a lower symmetry structure of C2 Al5 - , where all five aluminum atoms are located on the same side of the C2 unit, albeit slightly higher in energy compared to the D3h structure. These computations show that the D3h structure of C2 Al5 - is highly stable, exhibiting a large HOMO-LUMO gap.

Anion Photoelectron Spectroscopy and Theoretical Studies of Ge3n+1O (n = 1-3) Clusters with the C3v Symmetric Ge3 Structural Unit.

We investigate Ge3n+1O-/0 (n = 1-3) clusters using anion photoelectron spectroscopy and theoretical calculations. The results show that the lowest energy structure of Ge4O- is a bent Cs symmetric trigonal bipyramidal structure, while Ge4O has a C3v symmetric trigonal bipyramidal structure. Ge7O- has two coexisting low-lying isomers, the first one can be viewed as a Ge2O unit interacting with a Ge5 trigonal bipyramid, the second one can be regarded as an O atom interacting with a Ge7 pentagonal bipyramid; whereas Ge7O has a C3v symmetric structure with a Ge atom and an O atom capping a Ge6 trigonal antiprism from the bottom and top, respectively. The structures of Ge10O- and Ge10O can be obtained by adding an O atom to different binding sites of a C3v symmetric Ge10. Chemical bonding analyses of Ge3n+1O (n = 1-3) reveal that the O atom interacts with its neighboring three Ge atoms forming one 4c-2e σ bond and two 4c-2e π bonds in the top Ge3O trigonal pyramid, while the terminal Ge atom forms one 4c-2e σ bond in the bottom Ge4 trigonal pyramid. The large HOMO-LUMO gaps of Ge3n+1O (n = 1-3) indicate that they have good stabilities. Ab initio molecular dynamics simulations suggest that both Ge7O and Ge10O are dynamically stable in general at 300 and 500 K. The current work suggests that the C3v symmetric Ge3 units and the insertion growth pattern may be viable for constructing 1D germanium oxide nanostructures with the chemical formula of Ge3n+1O.

Structures and Properties of Planar Ge3O3 Cluster and Its Buckled Honeycomb Two-Dimensional Nanostructure.

The discovery of graphene and its excellent properties inspired the search for more two-dimensional (2D) materials. Understanding the structures and properties of the smallest repeating units as well as crystal 2D materials is helpful for designing 2D materials. As germanium tends to form three-dimensional structures, the preparation of germanium-based 2D nanomaterials is still a challenge. Herein, we report a Ge3O3 cluster with the potential to construct a germanium oxide 2D nanostructure. We conduct a combined anion photoelectron spectroscopy and theoretical study on Ge3O3-/0. The structure of Ge3O3- is a Cs symmetric nonplanar six-membered ring, while that of Ge3O3 is a D3h symmetric planar six-membered ring. Chemical bonding analyses reveal that Ge3O3 exhibits π aromaticity. First-principle results suggest that a buckled honeycomb 2D nanostructure with a wide band gap of 3.14 eV may be produced based on Ge3O3, which is promising in optoelectronic applications especially in blue, violet, and ultraviolet regions.

Solvation of magnesium chloride dimer in water: The case of anionic and neutral clusters.

The structures of magnesium chloride dimer-water clusters, (MgCl2)2(H2O)n-/0, were investigated with size-selected anion photoelectron spectroscopy and theoretical calculations to understand the dissolution of magnesium chloride in water. The most stable structures were confirmed by comparing vertical detachment energies (VDEs) with the experimental measurements. A dramatic drop of VDE at n = 3 has been observed in the experiment, which is in accordance with the structural change of (MgCl2)2(H2O)n-. Compared to the neutral clusters, the excess electron induces two significant phenomena in (MgCl2)2(H2O)n-. First, the planar D2h geometry can be converted into a C3v structure at n = 0, making the Mg-Cl bonds easier to be broken by water molecules. More importantly, a negative charge-transfer-to-solvent process occurs after adding three water molecules (i.e., at n = 3), which leads to an obvious deviation in the evolution of the clusters. Such electron transfer behavior was noticed at n = 1 in monomer MgCl2(H2O)n-, indicating that the dimerization between two MgCl2 molecules can make the cluster more capable of binding electron. In neutral (MgCl2)2(H2O)n, this dimerization provides more sites for the added water molecules, which can stabilize the entire cluster and maintain its initial structure. Specifically, filling the coordination number to be 6 for Mg atoms can be seen as a link between structural preferences in the dissolution of the monomers, dimers, and extended bulk-state of MgCl2. This work represents an important step forward into fully understanding the solvation of MgCl2 crystals and other multivalent salt oligomers.

Spectroscopy of Radicals, Clusters, and Transition States Using Slow Electron Velocity-Map Imaging of Cryogenically Cooled Anions

Slow electron velocity-map imaging of cryogenically cooled anions (cryo-SEVI) is a high-resolution variant of anion photoelectron spectroscopy that has been applied with considerable success over the years to the study of radicals, size-selected clusters, and transition states for unimolecular and bimolecular reactions. Cryo-SEVI retains the versatility of conventional anion photoelectron spectroscopy while offering sub-meV resolution, thereby enabling the resolution of vibrational structure in the photoelectron spectra of complex anions. This Feature Article describes recent experiments in our laboratory using cryo-SEVI, including a new research direction in which anions are vibrationally pre-excited with an infrared laser pulse prior to photodetachment.

Intramolecular Proton Transfer in the Radical Anion of Cytidine Monophosphate Sheds Light on the Sensitivities of Dry vs Wet DNA to Electron Attachment-Induced Damage.

Single-strand breaks (SSBs) induced via electron attachment were previously observed in dry DNA under ultrahigh vacuum (UHV), while hydrated electrons were found not able to induce this DNA damage in an aqueous solution. To explain these findings, crossed electron-molecular beam (CEMB) and anion photoelectron spectroscopy (aPES) experiments coupled to density functional theory (DFT) modeling were used to demonstrate the fundamental importance of proton transfer (PT) in radical anions formed via electron attachment. Three molecular systems were investigated: 5'-monophosphate of 2'-deoxycytidine (dCMPH), where PT in the electron adduct is feasible, and two ethylated derivatives, 5'-diethylphosphate and 3',5'-tetraethyldiphosphate of 2'-deoxycytidine, where PT is blocked due to substitution of labile protons with the ethyl residues. CEMB and aPES experiments confirmed the cleavage of the C3'/C5'-O bond as the main dissociation channel related to electron attachment in the ethylated derivatives. In the case of dCMPH, however, electron attachment (in the aPES experiments) yielded its parent (intact) radical anion, dCMPH-, suggesting that its dissociation was inhibited. The aPES-measured vertical detachment energy of the dCMPH- was found to be 3.27 eV, which agreed with its B3LYP/6-31++G(d,p)-calculated value and implied that electron-induced proton transfer (EIPT) had occurred during electron attachment to the dCMPH model nucleotide. In other words, EIPT, subduing dissociation, appeared to be somewhat protective against SSB. While EIPT is facilitated in solution compared to the dry environment, the above findings are consistent with the stability of DNA against hydrated electron-induced SSB in solution versus free electron-induced SSB formation in dry DNA.

Identification of Ge≡O Triple Bond in Ge6O– Cluster: Anion Photoelectron Spectroscopy and Theoretical Calculations

Unlike C≡O, which is common in coordination chemistry and organometallic chemistry, little is known about Si≡O or Ge≡O compounds. Here we report a Ge6O- cluster featuring a Ge≡O triple bond. The structural and chemical bonding properties of Ge6O-/0 are investigated using anion photoelectron spectroscopy and theoretical calculations. Two nearly degenerate isomers have been found for Ge6O-. The lowest-energy structure (6A) can be viewed as an O atom bonding with a tetragonal bipyramidal Ge6. The second one (6B) can be considered as an O atom interacting with a capped trigonal bipyramidal Ge6. Chemical bonding analyses reveal that Ge6O- (6A) can be viewed as a Ge≡O unit interacting with a σ antiaromatic C2v symmetric tetragonal pyramidal Ge53- moiety. Comparisons of the chemical bonding in Ge6O- (6A) with that in Ge5CO- and Ge5MnO- indicate the similar behavior of Ge≡O to C≡O and Mn≡O in its bonding to the Ge53- and Ge54- moieties.

Noncovalent chalcogen and tetrel bonding interactions: Spectroscopic study of halide–carbonyl sulfide complexes

AbstractChalcogen and tetrel intermolecular bonding interactions formed between carbonyl sulfide and halide anions have been studied utilizing a combined experimental and theoretical approach. In particular, high‐level CCSD(T) energetics and experimental anion photoelectron spectroscopy have been used in order to assign the dominant binding motif exhibited in these complexes. Halide anions solvated by multiple carbonyl sulfide molecules have also been investigated in order to ascertain the effect that additional binding partners has on the strength of the noncovalent interactions. The experimental and computational results support the main binding motif of carbonyl sulfide molecules with halide anions being chalcogen bonding, both in dimer complexes and larger solvated complexes. In addition, comparison between the noncovalent interactions formed by halides with carbon disulfide, carbonyl sulfide, and carbon dioxide allows a deeper understanding of noncovalent binding strength in relation to isoelectronic species.Key points Spectroscopic and ab initio characterization of halide–carbonyl sulfide van der Waals complexes bound through chalcogen and tetrel bonding. Detailed insight into chalcogen and tetrel bond strength in the context of changing chemical environments. Effect of increasing solvation on noncovalent binding strength.

Investigation of the Structures and Chemical Bonding of Mn2Ge6- and Mn2Ge7- Clusters via Anion Photoelectron Spectroscopy and Theoretical Calculations.

We present joint anion photoelectron spectroscopy and theoretical studies for Mn2Ge6- and Mn2Ge7-. Experimental results show that Mn2Ge6- and Mn2Ge7- have vertical electron detachment energies of 2.58 ± 0.08 and 2.88 ± 0.08 eV, respectively. Both Mn2Ge6- and Mn2Ge6 have Cs symmetric structures with a Mn atom attached to a pentagonal bipyramid MnGe6. Both Mn2Ge7- and Mn2Ge7 have C2v symmetric structures, which can be considered as two Mn2Ge4 tetragonal bipyramids sharing a MnGeMn face. According to chemical bonding analyses, Mn2Ge6 could be considered as a (MnII)(MnGe62-) complex. Theoretical calculations predict that the extension of Mn2Ge7 to Mn2nGe4n+3 may be able to produce a new type of Mn-doped germanium nanostructure.