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DFT Quantum Chemical Calculation of Metal Clusters

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Molecular Structure".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 7426

Special Issue Editor

Department of Analytical Chemistry, National Research Technological University, K. Marx Street 68, 420015 Kazan, Russia
Interests: coordination chemistry; quantum chemistry; chemistry of macrocyclic compounds; nanosciences; scientometrics
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

As you know, the term “cluster” is collective and includes substances that are quite diverse in composition and chemical structure. According to the classical definition of this term, the author of which was one of the world’s largest experts in the field of coordination chemistry, Prof. F.A. Cotton, clusters are chemical compounds containing a limited number of metal atoms, which are fully or largely covalently bonded to each other, even if the compound contains additional non-metal atoms that are part of any structural groups associated with metal atoms. Initially, this term referred almost exclusively to the coordination compounds of p-, d- and f-elements, but over time, more and more new compounds were included in it. At the present time, the concept of a “cluster” de facto includes chemical compounds that are intermediate between a molecule and a bulk solid with a wide variety of stoichiometric composition and geometric structures. Nevertheless, the clusters that fall under the above classical definition are as before of the greatest interest, since they have already found many applications in various fields of science and practice of anthropogenic activity, and their scope is expanding from year to year. In this connection, it becomes important to predict their physicochemical parameters that precisely determine these properties—a problem that is currently being successfully solved due to the availability of modern quantum-chemical calculation methods, as well as computer technologies and associated experimental equipment.

Taking into account the above, this Special Issue aims to include original full articles and short communications devoted to quantum-chemical calculations of all varieties of cluster compounds of p-, d-, and f-elements (inorganic, intermetallic, coordination ones with various organic and organo-element ligands) performed using different versions of the density functional theory (DFT) or with methods of a higher level. We welcome papers that, along with the necessary quantum-chemical calculations, will also present experimental data to assess the reliability of these calculations. Review articles may also be submitted for publication in this Special Issue (including author reviews, which focus on their authors’ own publications).

Prof. Dr. Oleg V. Mikhailov
Guest Editor

Manuscript Submission Information

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Keywords

  • DFT quantum-chemical calculation
  • Molecular structure
  • Thermodynamic characteristics
  • p-metal cluster
  • d-metal cluster
  • f-metal cluster
  • Cluster coordination compound
  • Intermetallic cluster

Published Papers (5 papers)

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Editorial

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3 pages, 162 KiB  
Editorial
Preamble from the Guest Editor of Special Issue “DFT Quantum-Chemical Calculation of Metal Clusters”
Molecules 2021, 26(2), 442; https://doi.org/10.3390/molecules26020442 - 15 Jan 2021
Viewed by 1126
Abstract
As known, the concept of “cluster” is collective and includes substances that are quite diverse in composition and chemical structure [...] Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)

Research

Jump to: Editorial

16 pages, 5032 KiB  
Article
Dimer Rhenium Tetrafluoride with a Triple Bond Re-Re: Structure, Bond Strength
Molecules 2023, 28(9), 3665; https://doi.org/10.3390/molecules28093665 - 23 Apr 2023
Cited by 1 | Viewed by 1112
Abstract
Based on the data of the gas electron diffraction/mass spectrometry (GED/MS) experiment, the composition of the vapor over rhenium tetrafluoride at T = 471 K was established, and it was found that species of the Re2F8 is present in the [...] Read more.
Based on the data of the gas electron diffraction/mass spectrometry (GED/MS) experiment, the composition of the vapor over rhenium tetrafluoride at T = 471 K was established, and it was found that species of the Re2F8 is present in the gas phase. The geometric structure of the Re2F8 molecule corresponding to D4h symmetry was found, and the following geometric parameters of the rh1 configuration were determined: rh1(Re-Re) = 2.264(5) Å, rh1(Re-F) = 1.846(4) Å, α(Re-Re-F) = 99.7(0.2)°, φ(F-Re-Re-F) = 2.4 (3.6)°. Calculations by the self-consistent field in full active space approximation showed that for Re2F8, the wave function of the 1A1g ground electronic state can be described by the single closed-shell determinant. For that reason, the DFT method was used for a structural study of Re2X8 molecules. The description of the nature of the Re-Re bond was performed in the framework of Atom in Molecules and Natural Bond Orbital analysis. The difference in the experimental values of r(Re-Re) in the free Re2F8 molecule and the [Re2F8]2− dianion in the crystal corresponds to the concept of a triple σ2π4 (ReIV-ReIV) bond and a quadruple σ2π4δ2 (ReIII-ReIII) bond, respectively, which are formed between rhenium atoms due to the interaction of d-atomic orbitals. The enthalpy of dissociation of the Re2F8 molecular form in two monomers ReF4dissH°(298) = 109.9 kcal/mol) and the bond energies E(Re-Re) and E(Re-X) in the series Re2F8→Re2Cl8→Re2Br8 molecules were estimated. It is shown that the Re-Re bond energy weakly depends on the nature of the halogen, while the symmetry of the Re2Br8 (D4d) geometric configuration differs from the symmetry of the Re2F8 and Re2Cl8 (D4h) molecules. Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)
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11 pages, 3599 KiB  
Article
Evolution of the Electronic Structure of the trans-[Re6S8bipy4Cl2] Octahedral Rhenium Cluster during Reduction
Molecules 2023, 28(9), 3658; https://doi.org/10.3390/molecules28093658 - 23 Apr 2023
Cited by 2 | Viewed by 912
Abstract
Understanding the processes that occur during the redox transformations of complexes coordinated by redox-active apical ligands is important for the design of electrochemically active compounds with functional properties. In this work, a detailed analysis of the interaction energy and electronic structure was performed [...] Read more.
Understanding the processes that occur during the redox transformations of complexes coordinated by redox-active apical ligands is important for the design of electrochemically active compounds with functional properties. In this work, a detailed analysis of the interaction energy and electronic structure was performed for cluster complexes trans-[Re6S8bipy4Cl2]n (n = 2–, 4–, 6–, 8–), which can be obtained by stepwise electrochemical reduction of a neutral cluster trans-[Re6S8bipy4Cl2] in DMSO solution. It was shown that the formation of open-shell paramagnetic ions with S = 1, 2 and 1 is the most energetically favorable for n = 2–, 4– and 6–, respectively. Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)
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11 pages, 3601 KiB  
Article
σ-Aromatic MAl6S6 (M = Ni, Pd, Pt) Stars Containing Planar Hexacoordinate Transition Metals
Molecules 2023, 28(3), 942; https://doi.org/10.3390/molecules28030942 - 17 Jan 2023
Cited by 3 | Viewed by 957
Abstract
Hypercoordinate transition-metal species are mainly dominated by the 18-valence-electron (18ve) counting. Herein, we report ternary MAl6S6 (M = Ni, Pd, Pt) clusters with the planar hexacoordinate metal (phM) centers, which feature 16ve counting instead of the classic 18ve rule. These [...] Read more.
Hypercoordinate transition-metal species are mainly dominated by the 18-valence-electron (18ve) counting. Herein, we report ternary MAl6S6 (M = Ni, Pd, Pt) clusters with the planar hexacoordinate metal (phM) centers, which feature 16ve counting instead of the classic 18ve rule. These global-minimum clusters are established via unbiased global searches, followed by PBE0 and single-point CCSD(T) calculations. The phM MAl6 units are stabilized by six peripheral bridging S atoms in these star-like species. Chemical bonding analyses reveal that there are 10 delocalized electrons around the phM center, which can render the aromaticity according to the (4n + 2) Hückel rule. It is worth noting that adding an (or two) electron(s) to its π-type lowest unoccupied molecular orbital (LUMO) will make the system unstable. Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)
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10 pages, 5751 KiB  
Article
Chirality and Relativistic Effects in Os3(CO)12
Molecules 2021, 26(11), 3333; https://doi.org/10.3390/molecules26113333 - 01 Jun 2021
Cited by 1 | Viewed by 2080
Abstract
The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os3(CO)12 with D3h and D3 symmetries using density functional theory (DFT) methods. The calculations took into account various levels of relativistic effects, [...] Read more.
The energy and structural parameters were obtained for all forms of the carbonyl complex of osmium Os3(CO)12 with D3h and D3 symmetries using density functional theory (DFT) methods. The calculations took into account various levels of relativistic effects, including those associated with nonconservation of spatial parity. It was shown that the ground state of Os3(CO)12 corresponds to the D3 symmetry and thus may be characterized either as left-twisted (D3S) or right-twisted (D3R). The D3S↔D3R transitions occur through the D3h transition state with an activation barrier of ~10–14 kJ/mol. Parity violation energy difference (PVED) between D3S and D3R states equals to ~5 × 10−10 kJ/mol. An unusual three-center exchange interaction was found inside the {Os3} fragment. It was found that the cooperative effects of the mutual influence of osmium atoms suppress the chirality of the electron system in the cluster. Full article
(This article belongs to the Special Issue DFT Quantum Chemical Calculation of Metal Clusters)
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