Hybrid Density Functionals for Clusters of Late Transition Metals: Assessing Energetic and Structural Properties

Soini, Thomas M.; Genest, Alexander; Nikodem, Astrid; Rösch, Notker

doi:10.1021/ct500703q

Cited by 23 publications

(75 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[37][38][39][40][41][42] To conrm our choice of functional and basis set, the possible structures for Au 3-10 were optimized and shown in Fig. S1.…”

Section: Resultsmentioning

confidence: 99%

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

et al. 2016

View full text Add to dashboard Cite

A detailed reaction mechanism of the triatomic gold cluster-catalyzed cycloisomerization of u-alkynylfuran was systemically investigated via density functional theory at the TPSSh/def2-TZVP level. The computational results indicated that the 5-exo Friedel-Crafts-type mechanism is the most favorable mechanism to form the phenol derivatives. The strong interaction between the gold and vinyl fragments in the Friedel-Crafts adduct is essential for the priority of the 5-exo Friedel-Crafts-type mechanism. Then, the 5-exo Friedel-Crafts-type mechanism on the various planar gold clusters (Au 4-10 ) was studied to clarify the size-effects of the planar gold clusters catalyzed u-alkynylfuran cycloisomerization. The appropriate interactions between the alkyne group in the substrate and gold clusters play a key role for the 5-exo cyclization step. The energy barriers of the ring-closure of the dienone carbene-gold intermediate step show an interesting "odd-even" behavior respective to the number of gold atoms. The Au 3 and Au 4 clusters are the most active catalysts for the u-alkynylfuran cycloisomerization to the phenol derivative. We also found that the active catalyst of the u-alkynylfuran cycloisomerization catalyzed by the gold(I) complexes should be the gold(0) complexes of the in situ generation. The catalytic activity of the gold(0) complex is comparable with that of the planar gold clusters. These findings may guide the rational design of highly active gold catalysts for the u-alkynylfuran cycloisomerization to phenol derivatives. † Electronic supplementary information (ESI) available: Fig. S1-S15, Tables S1-S9, details of the energy decomposition analysis, and the Cartesian coordinates, single point electronic energies (in the gas phase and acetonitrile), zero-point, and free energy correction for all of the stationary points and imaginary frequencies of transition structures. See Scheme 2 Different transition metal complex-catalyzed-u-alkynylfurans cycloisomerizations.Scheme 3 Proposed mechanism for the gold-catalyzed phenol synthesis.

show abstract

“…[37][38][39][40][41][42] To conrm our choice of functional and basis set, the possible structures for Au 3-10 were optimized and shown in Fig. S1.…”

Section: Resultsmentioning

confidence: 99%

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

et al. 2016

View full text Add to dashboard Cite

show abstract

“…27,38 The possible effects of different mixing percentage of HF potential of the sX and HSE06 still cannot be ruled out. In terms of pure metal surfaces, Soini et al 56 found that the smaller HF mixing percentage in the TPSSh hybrid functional, compared with 20% HF in B3LYP and 25% HF in PBE0, offers a reasonable compromise between the self-interaction corrections and static correlation that it yields an overall good description of the late transition metal clusters. In terms of CO adsorbate on Pt(111) surface, Ref.…”

Section: -9mentioning

confidence: 99%

The screening effects of the screened exchange hybrid functional in surface systems: A case study on the CO/Pt(111) problem

2016

View full text Add to dashboard Cite

The screened exchange (sX) hybrid functional has been widely used in computational material science. Although it has widely been studied in bulk systems, less is known about its functional behavior in surface systems which are crucial to many technologies such as materials synthesis and nano-electronic devices. Assessing the screening dependent functional behaviors in the surface systems is therefore important for its application in such systems. In this work, we investigate the screening effects of the sX in CO adsorption on Pt(111) surface. The differences between the sX and Heyd-Scuseria-Ernzerhof (HSE06) hybrid functionals, and the effects of screening parameters are studied. The screening has two effects: first, the HOMO-LUMO gap is screening dependent. This affects the site preference most significantly. In this work, atop adsorption of CO/Pt (111) is predicted by the hybrid functionals with screened exchange potential. The sX(1.44) gives the largest HOMO-LUMO gap for the isolated CO molecule. The adsorption energy difference between the atop and fcc site is also the largest by the sX(1.44) which is explained by the reduced metal d states to the CO 2π* state back-donation, with stronger effect for the fcc adsorption than for the atop adsorption; second, the adsorption energy is screening dependent. This can be seen by comparing the sX(2.38) and HSE06 which have different screening strengths. They show similar surface band structures for the CO adsorption but different adsorption energies, which is explained by the stronger CO 5σ state to the metal d states donation or the effectively screened Pauli repulsion. This work underlines the screening strength as a main difference between sX and HSE06, as well as an important hybrid functional parameter for surface calculation. C 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license

show abstract

“…6,[15][16][17] The economical relevance 18 of industrial applications represents an especially strong driving force for scientific research aiming at a detailed understanding of the properties of TM clusters and NPs. 3,[38][39][40][41][42][43][44][45][46][47][48][49][50][51] Indeed, the physical and chemical properties of such systems follow scaling laws as they slowly approach their corresponding bulk limits. 16,[19][20][21][22][23][24] In such combined studies the experimentally examined systems need to be as close as possible to the models used in the corresponding computational studies.…”

Section: Notker Röschmentioning

confidence: 99%

“…Often enough, synergy effects resulting from joint experimental and computational studies turn out to be essential for gaining insights at the atomic level. 3,[39][40][41][42][43][44][45][46][47][48][49][50][51] The onset of this latter scaling behavior, hence the beginning of the so-called scalable regime, is smooth and the cluster sizes at which it occurs depend on the atomic element of the particles at hand and the property under study. With regard to nanocatalysis 6,[25][26][27] this requirement can impose considerable problems as the catalytically active species employed in industrial processes often are significantly larger than the computational models for which accurate calculations are feasible, 24,25 e.g., by means of Kohn-Sham (KS) density functional theory (DFT).…”

Section: Notker Röschmentioning

confidence: 99%

“…With regard to nanocatalysis 6,[25][26][27] this requirement can impose considerable problems as the catalytically active species employed in industrial processes often are significantly larger than the computational models for which accurate calculations are feasible, 24,25 e.g., by means of Kohn-Sham (KS) density functional theory (DFT). [39][40][41][42][43][44][45][46][47][48][49][50][51] From results for a series of such medium-sized clusters, scaling laws (Section 2.1) then can be invoked to extrapolate the properties of much larger NPs. 9,24 Modern cluster sources based on sputtering, 29 laser vaporization, 30,31 pulsed microplasma, 32 or discharge techniques 33 can generate particles in a wide range of sizes, but specific mass-selection is only guaranteed for species consisting of a few atoms.…”

Section: Notker Röschmentioning

confidence: 99%

See 1 more Smart Citation

Size-dependent properties of transition metal clusters: from molecules to crystals and surfaces – computational studies with the program ParaGauss

Soini

Rösch

2015

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

In the so-called scalable regime the size-dependent behavior of the physical and chemical properties of transition metal clusters is described by scaling relationships. For most quantities this scalable regime is reached for cluster sizes between a few tens and a few hundreds of atoms, hence for systems for which an accurate treatment by density functional theory is still feasible. Thus, by invoking scaling relations one is able to obtain properties of very large nanoparticles and even the bulk limit from the results of a series of smaller cluster models. In this invited review we illustrate this strategy by exploiting results from computational studies that mostly were carried out with the density functional theory software ParaGauss. We address mainly the size-dependent behavior of the properties of transition metal clusters. To this end, we first present benchmark studies probing various approximations that are used in such density functional calculations. Subsequently we show how physical insight may be gained by exploring less understood types of systems. These applications range from bare clusters to nanoislands and nanoalloys to adsorption complexes.

show abstract

Hybrid Density Functionals for Clusters of Late Transition Metals: Assessing Energetic and Structural Properties

Cited by 23 publications

References 79 publications

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

The screening effects of the screened exchange hybrid functional in surface systems: A case study on the CO/Pt(111) problem

Size-dependent properties of transition metal clusters: from molecules to crystals and surfaces – computational studies with the program ParaGauss

Contact Info

Product

Resources

About