Probing the Electronic Properties of W3Ox–/0 (x = 0–2) and W32– Clusters: The Aromaticity of W3 and W32–

Lin, Shengnan; Zhang, Xian-Hui; Xu, Lei; Wang, Bin; Zhang, Yongfan; Huang, Xin

doi:10.1021/jp400673s

Cited by 16 publications

(3 citation statements)

References 75 publications

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“…The Hf 3 ( 1 A 1 ′ D 3 h ) cluster was shown to exhibit a triple σ, π, and δ aromaticity . The δ aromatic character was identified by canonical MO analysis and negative NICS value for the W 3 2– and W 3 O 9 2– clusters. , In the latter, a combination of 5d-AOs of W atoms produces delocalized MOs that turn out to be responsible for a δ aromaticity with two delocalized electrons. The 5d-AOs generate delocalized δ MOs occupied by two electrons in the anion Ta 3 – and its oxides including Ta 3 O – and Ta 3 O 3 – .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

et al. 2016

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Geometry, chemical bonding, and aromatic feature of a series of small silver clusters doped by an Sc atom (ScAg with n = 1-7) were investigated by means of density functional theory calculations. A planar shape is found for ScAg including n from 4 to 7. The growth mechanism is established for the formation of the hexagonal and heptagonal metallic cycles following increase of the number of Ag atoms. Particularly, both clusters ScAg and ScAg present a planar cyclic form in which the Sc atom is situated at the central position of the Ag and Ag cycles. The σ aromaticity is unambiguously demonstrated by the existence of strongly diatropic current flows within the ring in both ScAg and ScAg. The isovalent ScCu cluster has a similar ring current characteristic. In the Sc-doped ScAg clusters, a delocalized bonding pattern is found as a connector between the dopant Sc and the Ag host, as indicated by an ELI_D analysis.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

et al. 2016

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“…The correction term was calculated as δE = E 1 – E 2 – ε HOMO , where E 1 and E 2 are the total energies of the anion and the neutral cluster with the anionic equilibrium geometry, and ε HOMO represents the eigenvalue of the highest occupied molecular orbital (HOMO) of the anion. Note that the generalized Koopmans’ theorem has been demonstrated to predict theoretical VDEs in line with experimental PES results, − and has also been applied to calculate VDEs in many theoretical studies recently. − …”

Section: Methodsmentioning

confidence: 88%

Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO_n^–1/0 (n = 1–4) Clusters

et al. 2018

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The existence of abundant 4f electrons significantly increases the complexity and difficulty in precisely determining the geometric and electronic structures of the lanthanide oxide clusters. Herein, by combining the photoelectron imaging spectroscopy and density functional theory (DFT) calculations, the electronic structure of GdO was investigated. An electron affinity (EA) of 1.16 ± 0.09 eV is obtained, and the measured anisotropy parameter (β) provides direct experimental evidence about the orbital symmetry of the detached electron in GdO − . DFT calculations have been employed to acquire the optimized geometries of the GdO n −1/0 (n = 2−4) clusters, and multiple activated oxygen species, which are radical, peroxide, superoxide, triradical, and ozonide radical, are found in these oxide clusters. Simulated photoelectron spectra (PES) of the GdO n −1/0 (n = 2−4) clusters are examined, which may stimulate further experimental investigations on the gadolinium oxide clusters. In addition, the valence molecular orbitals (MOs) of these clusters are also discussed to reveal the interaction between the lanthanide metal (Gd) and O atoms.

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“…It is worth noting that δ electrons, which are formed by d–d interactions in metal clusters, are also of importance in some planar cycles. On the basis of canonical MO analysis and NICS calculations, a δ aromatic nature is identified for Hf 3 , W 3 2– , W 3 O 9 2– , Ta 3 – , Ta 3 O – , and Ta 3 O 3 – . − The more conventional π aromatic feature was identified for triangular cycles Zn 3 2– , Cd 3 2– , and Hg 3 2– by CMO analyses, and mostly by negative NICS values involving 2π electrons . Likewise, the existence of 10 delocalized π electrons confer to the [Fe(Sb) 5 ] + and [Fe(Bi) 5 ] + five-membered rings a clear π aromatic character …”

Section: Introductionmentioning

confidence: 98%

Aromaticity of Some Metal Clusters: A Different View from Magnetic Ring Current

Pham

Nguyen

2018

J. Phys. Chem. A

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The aromatic character of some small planar metallic clusters was revisited with an emphasis on their σ electrons. In contrast to previous reports, our approach based on magnetic ring current as an indicator for aromaticity points out that the σ electron delocalization in molecules behaves as an important contributor to their thermodynamic stability. Ring current maps were constructed using electron densities obtained from density functional theory calculations with the B3LYP functional and the 6-311G(d) basis set. Diatropic currents were further confirmed by an analysis of the symmetry of electronic excitations involved. The triatomic B cycle is found to maintain a double σ and π aromaticity when it forms the [B(NN)] and [B(CO)] complexes. The planar pentacoordinated carbon clusters including C@Al, C@AlBe, C@BeH, C@BeLi, and C@BeHLi are σ aromatic rather than π aromatic as previously assigned. The mixed copper clusters CuSi and CuGe are found to be σ aromatic compounds. The copper hydrides CuH can better be regarded as nonaromatic rather than aromatic compounds. The ring current indicator reveals the σ aromatic feature for Be@BeH and Be@BeH clusters, whereas this criterion shows a double aromaticity of Be@B and Be@B. Overall, the present study points out again the importance of σ electrons in determining the bonding characteristics of metallic clusters, and they should equally be considered as a key element.

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Probing the Electronic Properties of W₃O_x^–/0 (x = 0–2) and W₃^2– Clusters: The Aromaticity of W₃ and W₃^2–

Cited by 16 publications

References 75 publications

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO_n^–1/0 (n = 1–4) Clusters

Aromaticity of Some Metal Clusters: A Different View from Magnetic Ring Current

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Probing the Electronic Properties of W3Ox–/0 (x = 0–2) and W32– Clusters: The Aromaticity of W3 and W32–

Cited by 16 publications

References 75 publications

Theoretical Study of Small Scandium-Doped Silver Clusters ScAgn with n = 1–7: σ-Aromatic Feature

Theoretical Study of Small Scandium-Doped Silver Clusters ScAgn with n = 1–7: σ-Aromatic Feature

Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdOn–1/0 (n = 1–4) Clusters

Aromaticity of Some Metal Clusters: A Different View from Magnetic Ring Current

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Probing the Electronic Properties of W₃O_x^–/0 (x = 0–2) and W₃^2– Clusters: The Aromaticity of W₃ and W₃^2–

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

Theoretical Study of Small Scandium-Doped Silver Clusters ScAg_n with n = 1–7: σ-Aromatic Feature

Probing the Geometric and Electronic Structures of the Monogadolinium Oxide GdO_n^–1/0 (n = 1–4) Clusters