The accuracy of the pseudopotential approximation. II. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InCl

Leininger, Thierry; Nicklass, Andreas; Stoll, Hermann; Dolg, Michael; Schwerdtfeger, Peter

doi:10.1063/1.471950

Cited by 513 publications

(321 citation statements)

References 34 publications

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“…Ref. 18 for a thorough discussion in a molecular context. This does not mean, on the other hand, that large-core pseudopotentials should not be applied at all for Zn and Cd.…”

Section: Hartree-fock Calculationsmentioning

confidence: 99%

Correlatedab initiocalculations for ground-state properties of II-VI semiconductors

1997

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Correlated ab-initio ground-state calculations, using relativistic energy-consistent pseudopotentials, are performed for six II-VI semiconductors. Valence (ns, np) correlations are evaluated using the coupled cluster approach with single and double excitations. An incremental scheme is applied based on correlation contributions of localized bond orbitals and of pairs and triples of such bonds. In view of the high polarity of the bonds in II-VI compounds, we examine both, ionic and covalent embedding schemes for the calculation of individual bond increments. Also, a partitioning of the correlation energy according to local ionic increments is tested. Core-valence (nsp, (n − 1)d) correlation effects are taken into account via a core-polarization potential. Combining the results at the correlated level with corresponding Hartree-Fock data we recover about 94% of the experimental cohesive energies; lattice constants are accurate to ∼1%; bulk moduli are on average 10% too large compared with experiment.

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“…Ref. 18 for a thorough discussion in a molecular context. This does not mean, on the other hand, that large-core pseudopotentials should not be applied at all for Zn and Cd.…”

Section: Hartree-fock Calculationsmentioning

confidence: 99%

Correlatedab initiocalculations for ground-state properties of II-VI semiconductors

1997

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“…59 For Ru we used the small-core, quasi-relativistic Stuttgart/Dresden effective core potential, with an associated valence basis set contracted (standard SDD keywords in Gaussian 09). 60,61,62 The geometry optimizations were performed without symmetry constraints, and the characterization of the located stationary points was performed by analytical frequency calculations.…”

Section: Methodsmentioning

confidence: 99%

Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst

et al. 2015

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ABSTRACT:A new bis-facial dinuclear ruthenium complex, {[Ru II (bpy)] 2 (μ-bimp)(μ-Cl)} 2+ , 2 2+ , containing a hexadentate pyrazolate-bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[Ru II (bpy)(H 2 O)] 2 (μ-bimp)} 3+ , 3 3+ , results in low efficiencies and selectivities when oxidizing water, but is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min -1 , are achieved using PhIO as oxidant. Moreover, 3 3+ presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on DFT calculations in order to better understand the putative cooperative effects within this dinuclear catalyst.The epoxidation of olefins, a process of great industrial and economical importance, has historically constituted a great challenge for the organic synthetic chemists. 1,2 Epoxides constitute a family of essential chemicals, particularly for the synthesis of various polymers (polyglycols, polyamides, polyurethanes, etc.), 3,4 and fine chemicals such as pharmaceuticals, food additives or flavor and fragrance compounds. 5 For instance, propylene oxide monopolizes the epoxide chemical business with a yearly 8 million Ton production and an expected annual increase of 5%. 6 Ru complexes are excellent catalysts for redox transformations such as alcohol oxidation, 7,8,9,10,11,12,13,14 sulfoxidation, 15,16,17,18 water oxidation 19,20,21,22,23,24,25,26,27,28 and epoxidation. 14,29,30,31,32,33,34,35,36,37 In all these cases, a Ru IV =O or Ru V =O group has been shown to be the active catalytic unit. Most of the literature related to redox catalysis using Ru complexes is based on mononuclear complexes, since they are generally easily accessible from a synthetic point of view. In sharp contrast, two powerful diruthenium epoxidation catalysts in terms of epoxide selectivity and substrate conversion have been recently reported by our research group. 38,39 In addition, these new catalysts display distinctive reactivity with regards to cis and trans alkenes. Both features are proposed to be caused by a hydrogen bonding interaction between the second Ru IV =O site and the substrate employed, together with steric effects.Our group has an extensive experience on the synthesis, characterization and evaluation of the oxidative catalytic performance of dinuclear Ru complexes, most of them inspired by the well-known {[Ru II (trpy)] 2 (μ-bpp)(μ-Cl)} 2+ water oxidation catalyst. 40 Modifications around this paradigmatic compound, like the replacement of the trpy auxiliary ligands by facially coordinating ...

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“…The electronic configuration of the molecular systems was described with the triple zeta valence polarization function of Ahlrichs and co-workers for H, C, N, P, and Cl (TZVP keyword in Gaussian) [51]. Cobalt, iron, and ruthenium were described by the small-core, quasi-relativistic Stuttgart/Dresden effective core potential, with an associated valence basis set, contracted (standard SDD keywords in Gaussian09) [52][53][54]. The geometry optimizations were performed without symmetry constraints, and the characterization of the located stationary points was achieved by analytical frequency calculations, using the BP86 functional of Becke and Perdew [32][33][34], together with the Grimme D3BJ correction term to the electronic energy [55,56].…”

Section: Computational Detailsmentioning

confidence: 99%

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

et al. 2017

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Density functional theory (DFT) calculations have been used to investigate the behavior of different transition metals from Groups 8 (Fe and Ru) and 9 (Co and Rh) in an already well-known catalytic mechanism, which is based on an Ru(SIMes)(PPh 3 )Cl 2 =CH(Ph) complex. As expected, Ru has proven to perform better than their Fe, Co, and Rh counterparts. Even though the topographic steric maps analysis shows no difference in sterical hindrance for any of the metal centers, geometrically, the Fe-based species show a high rigidity with shorter and stronger bonds confirmed by Mayer Bond Orders. The systems bearing Co as a metallic center might present a reactivity that is, surprisingly, too high according to conceptual DFT, which would consequently be a drawback for the formation of the fundamental species of the reaction pathway: the metallacycle intermediate.

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The accuracy of the pseudopotential approximation. II. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InCl

Cited by 513 publications

References 34 publications

Correlatedab initiocalculations for ground-state properties of II-VI semiconductors

Correlatedab initiocalculations for ground-state properties of II-VI semiconductors

Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst

In Silico Switch from Second- to First-Row Transition Metals in Olefin Metathesis: From Ru to Fe and from Rh to Co

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