Size evolution relativistic DFT-QTAIM study on the gold cluster complexes Au4-S-CnH2n-S′-Au4′ (n = 2–5)

Rodríguez, Juan I.; Uribe, Emilbus A.; Baltazar-Méndez, María I.; Autschbach, Jochen; Castillo-Alvarado, F. L.; Gutiérrez-González, Israel

doi:10.1016/j.cplett.2016.08.038

Cited by 11 publications

(11 citation statements)

References 47 publications

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“…These extra bonds can be classified as non‐covalent because ∇ 2 ρ ( r )≃0.03>0 (see Table ) with a bond length of about 2.8 Å. Notice however that this value of the Laplacian is one order of magnitude lower than the corresponding value of the other non‐covalent bonds Au⋅⋅⋅Au in the gold nanocluster [∇ 2 ρ ( r )≃0.1>0, see Table ], which also were reported previously in similar complex systems . In addition to these two extra BCPs (bonds), two RCBs also appear in the ZORA relativistic case (see Figure ).…”

Section: Resultssupporting

confidence: 73%

“…However, some of the authors of this work have recently showed that the gold cluster might be bonding directly with the benzene in addition to the sulfur . The precise nature of the chemical bonding between gold and the organic molecule in these complex systems remains unclear, and elucidating it is one of the goals of this work …”

Section: Introductionmentioning

confidence: 98%

“…Using a single organic molecule as a wire (conductor) has been the research topic of many experimental and theoretical works in the field of the so‐called molecular electronics . A dithiol linking two gold clusters (like the systems studied here) has been previously studied due to the special properties of gold nanoclusters and its preferential bonding with sulfur in self‐assembled monolayers and passivated gold nanoclusters by thiols . The chemical bonding between sulfur and gold plays an important role as a bridge between the organic and the metallic part.…”

Section: Introductionmentioning

confidence: 99%

“…To demonstrate this, in this study we consider a gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 (see Figure ), and show how sensitive its topology is to various physical phenomena. Specifically, new bond paths between hydrogen and gold (H1 and Au4; H2 and Au8) appear upon the inclusion of relativistic effects.…”

Section: Introductionmentioning

confidence: 99%

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Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Anderson

Rodríguez

Ayers

et al. 2019

Chemistry A European J

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The topology of the molecular electron density of benzene dithiol gold cluster complex Au4−S−C6H4−S′−Au′4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.

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Section: Resultssupporting

confidence: 73%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Anderson

Rodríguez

Ayers

et al. 2019

Chemistry A European J

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“…Another important contribution of Latin America researchers was performed by Rodríguez et al In such study, the chemical interactions displayed by gold cluster complexes

((),, {Au}_{4} H_{2 n} - S^{'} - normalA u_{4}^{'}, n = 2 - 5)

were characterized by means of relativistic‐ZORA QTAIM. One of the most standout results was the fact that Au–Au and S–Au bonds displayed noncovalent characteristics, showing closed shell interactions characterized by positive values of the Laplacian of the electron density at the BCP.…”

Section: Further Developments In Qctmentioning

confidence: 99%

Latin American contributions to quantum chemical topology

García‐Revilla

Cortés‐Guzmán

Rocha‐Rinza

et al. 2018

Int J of Quantum Chemistry

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We survey the contributions from Latin American theoretical chemists to the field of quantum chemical topology (QCT) over nearly the last 30 years with emphasis on the developments and applications of the quantum theory of atoms in molecules (QTAIM). Applications of QCT in the fields of excited states, electron delocalization, chemical bond, aromaticity, conformational analysis, spectroscopic properties, and chemical reactivity are presented. We also consider the coupling of QTAIM with time‐dependent density functional theory, the virial theorem in the Kohn‐Sham method and the inclusion of electron dynamical correlation in the interacting quantum atoms method using coupled cluster and multi‐configurational densities. Additionally, we describe the development of efficient algorithms for the calculation of topological properties derived from the electron density. This review is aimed not only at providing an account of the contributions to QCT in Latin America but also at stimulating guides for further progress in the field.

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Quantum chemical topology at the spin–orbit configuration interaction level: Application to astatine compounds

et al. 2020

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We report a methodology that allows the investigation of the consequences of the spin-orbit coupling by means of the QTAIM and ELF topological analyses performed on top of relativistic and multiconfigurational wave functions. In practice, it relies on the "state-specific" natural orbitals (NOs; expressed in a Cartesian Gaussian-type orbital basis) and their occupation numbers (ONs) for the quantum state of interest, arising from a spin-orbit configuration interaction calculation. The ground states of astatine diatomic molecules (AtX with X = At F) and trihalide anions (IAtI − , BrAtBr − , and IAtBr −) are studied, at exact two-component relativistic coupled cluster geometries, revealing unusual topological properties as well as a significant role of the spinorbit coupling on these. In essence, the presented methodology can also be applied to the ground and/or excited states of any compound, with controlled validity up to including elements with active 5d, 6p, and/or 5f shells, and potential limitations starting with active 6d, 7p, and/or 6f shells bearing strong spin-orbit couplings.

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Size evolution relativistic DFT-QTAIM study on the gold cluster complexes Au4-S-CnH2n-S′-Au4′ (n = 2–5)

Cited by 11 publications

References 47 publications

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

Latin American contributions to quantum chemical topology

Quantum chemical topology at the spin–orbit configuration interaction level: Application to astatine compounds

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