Reference Vertical Excitation Energies for Transition Metal Compounds

To enrich and enhance the diversity of the \textsc{quest} database of highly-accurate excitation energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril \textit{et al.}, \textit{WIREs Comput.~Mol.~Sci.}~\textbf{11}, e1517 (2021)}], we report vertical transition energies in transition metal compounds. Eleven diatomic molecules with singlet or doublet ground state containing a fourth-row transition metal (\ce{CuCl}, \ce{CuF}, \ce{CuH}, \ce{ScF}, \ce{ScH}, \ce{ScO}, \ce{ScS}, \ce{TiN}, \ce{ZnH}, \ce{ZnO}, and \ce{ZnS}) are considered and the corresponding excitation energies are computed using high-level coupled-cluster (CC) methods, namely CC3, CCSDT, CC4, and CCSDTQ, as well as multiconfigurational methods such as CASPT2 and NEVPT2. In some cases, to provide more comprehensive benchmark data, we also provide full configuration interaction estimates computed with the \textit{"Configuration Interaction using a Perturbative Selection made Iteratively"} (CIPSI) method. Based on these calculations, theoretical best estimates of the transition energies are established in both the aug-cc-pVDZ and aug-cc-pVTZ basis sets. This allows us to accurately assess the performance of CC and multiconfigurational methods for this specific set of challenging transitions. Furthermore, comparisons with experimental data and previous theoretical results are also reported.Comment: 17 pages, 3 figure

Modélisation de clusters stables contenant des métaux de transition du groupe 11

The work described in this manuscript concerns electronic structure calculations of homo- and hetero-nuclear clusters made of group 11 metals, in order to rationalize their stability, structure and in some cases properties. We have first looked at the fact that copper superatoms are very scarce, contrarily to their gold and silver counterparts. Our calculations indicate that copper superatoms are more stable than silver superatoms. However, the synthetic process based on the reduction of Cu(I) complexes by borohydride leads preferentially to the formation of very stable Cu(I) polyhydrides. On the other hand, we have looked at the stability of clusters containing a tetrahedral M₁₆ core similar to the one contained in the emblematic [Au₂₀] cluster. Our investigation of the 20-electron organometallic clusters [M₁₆Ni₂₄(CO)₄₀]⁴⁻ (M = group 11) showed that the four peripheral Ni₆(CO)₁₀ units are full part of the superatom entity, suggesting that the [M₁₆]⁴⁻ entity is not viable. Calculations on several homo- and hetero-nuclear series of bare species indicate that this instability can be avoided either in reducing the electron count to 18, or in incorporating a supplementary element in cluster center. In another investigation, we explored the possibility of doping the icosahedral 18-electron [WAu₁₂] cluster by 0-electron donor platinum atoms, namely [WAu₁₂Pdₓ] (x = 1-4). Calculations indicate that some isomers are stable and have a large spectrum of UV-vis absorption, providing them potential applications. Finally, we have investigated the electronic structure of organometallic clusters, [Cu₃Zn₄Cp*5] and [Cu₂Zn₅Cp*₅]⁺, which are apparently extremely electron-deficient and showed that this deficiency is not as large as it appears.Les travaux décrits dans ce mémoire portent sur le calcul de la structure électronique de clusters homo- ou hétéro-nucléaires de métaux du groupe 11, afin d’en interpréter leur stabilité, leur structure et éventuellement leurs propriétés. Nous nous sommes tout d’abord intéressés au fait que, contrairement à leurs homologues de l’or et de l’argent, les superatomes de cuivre sont très rares. Nos calculs montrent que ces derniers sont plus stables que les superatomes d’argent. Néanmoins, les méthodes de synthèse de superatomes par réduction de complexes de Cu(I) par le borohydrure conduisent préférentiellement à la formation de polyhydrures de Cu(I) en raison de leur grande stabilité. Nous nous sommes de plus intéressés à la stabilité de clusters contenant un cœur tétraédrique M16, analogue à celui contenu dans le cluster emblématique [Au₂₀]. Notre étude des clusters organométalliques à 20 électrons. [M₁₆Ni₂₄(CO)₄₀]⁴⁻ (M = groupe 11) indiquent que les quatre entités périphériques Ni₆(CO)₁₀ font partie intégrante du superatome, suggérant que [M₁₆]⁴⁻ n’est pas viable. Des calculs sur plusieurs séries de systèmes homo- ou hétéro-nucléaires nus proposent de contourner cet écueil soit en réduisant le nombre d’électrons à 18, soit en incorporant un élément encapsulé au centre de l’entité tétraédrique. Dans une autre étude, nous avons exploré la possibilité de dopage du cluster icosaèdrique à 18 électrons [WAu₁₂] par des atomes de platine (donneurs de 0 électron), soit [WAu₁₂Pdₓ] (x = 1-4). Le calcul indique que certains isomères sont viables et présentent un large spectre d’absorption UV-vis leur conférant des applications potentielles. Enfin, nous avons étudié la structure électronique de clusters organométalliques apparemment très déficitaires en électrons, [Cu₃Zn₄Cp*5] et [Cu₂Zn₅Cp*₅]⁺ et montré que ce déficit n’est aussi important qu’il n’apparaît

Electron Counting in Ligated High Nuclearity Late Transition Metal Clusters

International audienceOver the years, the development of large ligated transition metal clusters has been accompanied by the development of theories using conceptual ideas and models which resulted in a range of electron-counting rules. All of them aimed to understand and rationalize the relationship between the structure and the electron count. Among these rules, those relying on the spherical jellium approximation, initially employed to study simple spherical alkali clusters, have shown to be very powerful to chemists interested in viewing ligated noble metal nanoclusters as superatoms, supermolecules or specific nano-objects with "magic" electron counts. This review develops the basic theory and illustrates its applications for specific spherical and non-spherical ligand-protected nanoclusters containing metals from groups 10 and 11

Reference Vertical Excitation Energies for Transition Metal Compounds

16 pages, 3 figuresTo enrich and enhance the diversity of the \textsc{quest} database of highly-accurate excitation energies [\href{https://doi.org/10.1002/wcms.1517}{V\'eril \textit{et al.}, \textit{WIREs Comput.~Mol.~Sci.}~\textbf{11}, e1517 (2021)}], we report vertical transition energies in transition metal compounds. Eleven diatomic molecules with singlet or doublet ground state containing a fourth-row transition metal (\ce{CuCl}, \ce{CuF}, \ce{CuH}, \ce{ScF}, \ce{ScH}, \ce{ScO}, \ce{ScS}, \ce{TiN}, \ce{ZnH}, \ce{ZnO}, and \ce{ZnS}) are considered and the corresponding excitation energies are computed using high-level coupled-cluster (CC) methods, namely CC3, CCSDT, CC4, and CCSDTQ, as well as multiconfigurational methods such as CASPT2 and NEVPT2. In some cases, to provide more comprehensive benchmark data, we also provide full configuration interaction estimates computed with the \textit{``Configuration Interaction using a Perturbative Selection made Iteratively''} (CIPSI) method. Based on these calculations, theoretical best estimates of the transition energies are established in both the aug-cc-pVDZ and aug-cc-pVTZ basis sets. This allows us to accurately assess the performance of CC and multiconfigurational methods for this specific set of challenging transitions. Furthermore, comparisons with experimental data and previous theoretical results are also reported

Stabilizing heteroatom-centered 16-vertex group 11 tetrahedral architectures Bonding and structural considerations toward versatile endohedral species

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Reinvestigation of the Total Li + /H + Ion Exchange on the Garnet-Type Li 5 La 3 Nb 2 O 12

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Symmetry lowering by cage doping in spherical superatoms Evaluation of electronic and optical properties of 18-electron W@Au12Ptn (n=0-4) superatomic clusters from relativistic DFT calculations

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Potential to stabilize 16-vertex tetrahedral coinage-metal cluster architectures related to Au-20

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[M16Ni24(CO)(40)](4-) Coinage Metal Tetrahedral Superatoms as Useful Building Blocks Related to Pyramidal Au-20 Clusters (M = Cu, Ag, Au). Electronic and Bonding Properties from Relativistic DFT Calculations

International audienceCharacterization of the tetrahedral Au-20 structure in the gas phase remains a major landmark in gold cluster chemistry, where further efforts to stabilize this bare 20-electron superatom in solution to extend and understand its chemistry have failed so far. Here, we account for the structural, electronic, and bonding properties of [M16Ni24(CO)(40)](4-) (M = Cu, Ag, Au) observed in solution for gold and silver. Our results show a direct electronic relationship with Au20, owing that such species share a common tetrahedral [M-16](4-) central core with a 1S(21)P(61)D(10)2S(2) jellium configuration. In the case of Au-20, the [Au-16](4-) core is capped by four Au+ ions, whereas in [M(16N)i(24)(CO)(40)](4-) it is capped by four Ni-6(CO)(10) units. In both cases, the capping entities are a full part of the superatom entity, where it appears that the free (uncapped) [M-16](4-) species must be capped for further stabilization. It follows that the Ni-6(CO)(10) units in [M16Ni24(CO)(40)](4-) should not be considered as external ligands as their bonding with the [M-16](4-) core is mainly associated with a delocalization of the 20 jellium electrons onto the Ni atoms. Thus, the [M16Ni24(CO)(40)](4-) species can be seen as the solution version of tetrahedral M-20 clusters, encouraging experimental efforts to further develop the chemistry of such complexes as M(111) finite surface section structures, with M = Ag and Au and, particularly promising, with M = Cu. Furthermore, optical properties were simulated to assist future experimental characterization

DFT study of inter-ring haptotropic rearrangement in CpRu+ complexes of polycyclic aromatic ligands

International audienceInter-ring haptotropic rearrangements (IRHRs) of different types are well-known phenomena in organometallic and catalytic chemistry. So far, they are reported for transition metal complexes with carbo-and heterocyclic polyaromatic hydrocarbons (PAH) of small and medium size. Here, we report DFT studies of RuCp+ shifts between neighboring six-membered rings (eta(6) reversible arrow eta(6)-IRHR) on an extra-large PAH as a model for graphene and compare it to naphthalene. Our calculations predict that eta(6) reversible arrow eta(6)-IRHRs proceed with much lower activation energy barrier of rearrangement in the case of the RuCp+ complex of eta(6)-graphene model