Greatly Enhanced Electron Affinities of Au2nCl Clusters (n = 1–4): Effects of Chlorine Doping

Ma, Yuan; Bian, Shen; Shi, Yingying; Fan, Xingting; Kong, Xianglei

doi:10.1021/acsomega.9b01981

Cited by 4 publications

(4 citation statements)

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“…The Au–F bond length remains close to 2 Å. It is interesting to note that the geometry of neutral Au 2 F is significantly different from that of neutral Au 2 Cl, which has a C 2 v symmetry . However, the geometries of anionic Au 2 F and Au 2 Cl are both linear.…”

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“…It is interesting to note that the geometry of neutral Au 2 F is significantly different from that of neutral Au 2 Cl, which has a C 2v symmetry. 31 However, the geometries of anionic Au 2 F and Au 2 Cl are both linear. The calculated EA of Au 2 F − is 4.12 eV, which agrees well with the experimental value of 4.17 eV in Table 1, validating our theoretical method.…”

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confidence: 99%

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Signature of Au as a Halogen

Shah

Banjade

Zhang

et al. 2022

J. Phys. Chem. Lett.

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Gold, although chemically inert in its bulk state, is reactive at the nanoscale and, in small clusters, even behaves like a hydrogen atom. Using a photoelectron spectroscopy experiment and first-principles theory, we show that Au also behaves like a halogen in small clusters. This is evident not only in strong resemblance between the photoelectron spectra of Au 2 F − and AuF 2 − but also in Au exhibiting one of the signature properties of halogens, its ability to form superhalogens with electron affinities higher than that of any halogen atom. For example, the electron affinity (EA) of Au 2 F − is 4.17 eV, while AuF 2 − , a known superhalogen, has an EA of 4.47 eV. Of particular interest is Au 2 F 2 , which, in spite of being a closed-shell system, is a pseudohalogen with an EA of 3.3 ± 0.1 eV. Here, one of the Au atoms behaves like a halogen, making Au 2 F 2 mimic the property of AuF 3 .G old, one of the most precious metals in the periodic table, has many faces. This is due to the relativistic effect, which stabilizes its 6s orbital while destabilizing its 5d orbitals. Chemically a transition metal belonging to the group 11 elements, Au, unlike its congeners Cu and Ag, is unreactive under ambient conditions and is considered to be a noble metal. However, gold is reactive at the nanometer length scale 1 and serves as an excellent catalyst. Analogous to transition metals, Au also exhibits multiple valences, with oxidation states ranging from −1 to +6, 2−5 oxidation states of +1 and +3 being the most prevalent. However, unlike transition metals, Au is not magnetic. Like hydrogen, Au has one electron in its outermost s shell. The fact that Au and H behave alike in small clusters was first suggested by Buckart et al., 6 who observed nearly identical features in the photoelectron spectra (PES) of Au n − and Au n−1 H − (n > 2). A similar conclusion was later reached by Wang and co-workers 7−9 when they examined the PES of binary silicon−gold clusters SiAu n (n = 2−4) and found these to be analogous to those of SiH n clusters. The gold− hydrogen analogy was also suggested by Ghanty, 10 who found similarities between new rare gas auride species and the corresponding hydrides. Later, the author 11 showed that the correspondence of the electronic structure, bonding, and stability of a new class of compounds AuBX (X = F, Cl, or Br) to those of HBX radicals is one to one.Note that Au and halogen atoms also have something in common; addition of an extra electron completes the 6s shell of the Au atom as it does the outer p shell of the halogen atoms. Indeed, with the exception of halogen atoms, the Au atom has the highest electron affinity (EA), namely, 2.31 eV, of any element in the periodic table. Au forms a salt with the Cs metal, with Cs carrying a positive charge and Au, like halogens,

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Signature of Au as a Halogen

Shah

Banjade

Zhang

et al. 2022

J. Phys. Chem. Lett.

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“…Therefore, understanding the structures of various series of gold chloride clusters, their growth pathways, and related kinetics is crucial for the growth of relevant gold nanoparticles. Despite the aforementioned studies on gold chloride clusters (Schwerdtfeger et al, 2004;Srivastava and Misra, 2014;Ma et al, 2019a;Ma et al, 2019b), there is still a gap in the study of polychlorinated gold cluster anions (for example, Au n Cl n+3 -) and their growth pathways. In this paper, we attempt to reveal the stability, structural regularity and cluster growth patterns of Au n Cl n+3 clusters by experimental methods and theoretical calculations.…”

Section: Introductionmentioning

confidence: 99%

Structures and growth pathways of AunCln+3- (n ≤ 7) cluster anions

Xu,

Liu,

Hou

et al. 2024

Front. Chem.

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Gold chloride clusters play an important role in catalysis and materials chemistry. Due to the diversity of their species and isomers, there is still a dearth of structural studies at the molecular level. In this work, anions of AunCln+3- and AunCln+5- (n = 2–4) clusters were obtained by laser desorption/ionization mass spectrometry (LDI MS), and the most stable isomers of AunCln+3- were determined after a thorough search and optimization at the TPSSh/aug-cc-pVTZ/ECP60MDF level. The results indicate that all isomers with the lowest energy have a planar zigzag skeleton. In each species, there is one Au(III) atom at the edge connected with four Cl atoms, which sets it from the other Au(I) atoms. Four growth pathways for AunCln+3- (n = 2–7) clusters are proposed (labelled R1, R2, R3 and R4). They are all associated with an aurophilic contact and are exothermic. The binding energies tend to stabilize at ∼ −41 kcal/mol when the size of the cluster increases in all pathways. The pathway R1, which connects all the most stable isomers of the respective clusters, is characterized by cluster growth due to aurophilic interactions at the terminal atom of Au(I) in the zigzag chains. In the pathway of R4 involving Au-Au bonding in its initial structures (n ≤ 3), the distance between intermediate gold atoms grows with cluster size, ultimately resulting in the transfer of the intermediate Au-Au bonding into aurophilic interaction. The size effect on the structure and aurophilic interactions of these clusters will be better understood based on these discoveries, potentially providing new insights into the active but elusive chemical species involved in the corresponding catalytic reactions or nanoparticle synthesis processes.

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“…, 20 Au n Ag m þ , 21 Au n Ar m þ , 22 AuC 3 H À , 23 and gold-chloride clusters. [24][25][26][27] The gold-chloride clusters were usually generated in the gas phase by using laser desorption ionization -LDI (the term laser ablation is often used) and HAuCl 4 as a gold source. Although the simplest Au(II) species, e.g.…”

Section: Introductionmentioning

confidence: 99%