σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity
Abstract
:1. Introduction
2. Theory
3. Computational Details
4. Results and Discussion
4.1. Exemplifying the Origin of the TM σs-Holes and σd-Holes—The TM2 and TM8 of Ir, Pt and Au
4.2. Local Lewis Acidic (and Basic) Characteristics of the TM13 Nanoclusters
4.2.1. Au13, Pt13 and Ir13
4.2.2. Rh13 and Ru13
4.2.3. Cu13 and Pt7Cu6
4.2.4. Pd13 and Co13
4.3. General Discussion
- Partially occupied d-orbitals
- Favorable electronic configuration (e.g., spin-state with low degree of spd-hybridization)
- Locally symmetric bonding arrangement (e.g., cubic)
5. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References and Notes
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Sym | (2S + 1) | AS | VS | ES | s-occ 1 | d-occ 1 | p-occ 1 | |
---|---|---|---|---|---|---|---|---|
Au13 | Cs | 2 | 10 | 10 | 9 | 0.73 | 9.90 | 0.38 |
Cu13 | C2 | 2 | 7 | 6 | 6 | 0.63 | 9.94 | 0.44 |
Pt13 | Cs | 3 | 7 | 15 | 15 | 0.61 | 9.08 | 0.32 |
Pt7Cu6 | C1 | 3 | 13 | 12 | 11 | 0.56 2 | 9.56 2 | 0.34 2 |
Pd13 | C2 | 9 | 7 | 7 | 8 | 0.37 | 9.34 | 0.29 |
Co13 | C3 | 28 | 4 | 4 | 3 | 0.65 | 7.82 | 0.52 |
Rh13 | Cs | 2 3 | 7 | 7 | 14 | 0.43 | 8.30 | 0.27 |
Ir13 | Cs | 4 | 10 | 17 | 15 | 0.67 | 7.97 | 0.37 |
Ru13 | Cs | 13 | 7 | 6 | 9 | 0.46 | 7.22 | 0.34 |
ASfav | VS,max | σtype | ES,min | ΔEint | dTM-O | dTM-σ | dσ-O | |
---|---|---|---|---|---|---|---|---|
Au13 | 13 | 16.80 | σs | −8.88 | −0.37 | 2.44 | 2.20 | 0.48 |
Cu13 | 1(2) | 19.55 | σs | −6.53 | −0.54 | 2.14 | 2.02 | 0.56 |
Pt13 | 12 | 20.12 | σd | −11.93 | −0.80 | 2.22 | 2.13 | 0.13 |
Pt7Cu6 | 1 1 | 35.38 | σs | −10.88 | −0.73 | 2.09 | 1.91 | 0.23 |
Pd13 | 8(11) 2 | 13.31 | σs | −5.14 | −0.59 | 2.28 | 2.16 | 1.35 |
Co13 | 8 3 | 21.65 | σs | −5.64 | −0.48 | 2.13 | 2.06 | 0.90 |
Rh13 | 1(7) | 20.43 | σd | −8.74 | −0.81 | 2.23 | 2.13 | 0.27 |
Ir13 | 6 | 33.75 | σs | −12.86 | −1.00 | 2.17 | 2.18 | 0.33 |
Ru13 | 3(1) 4 | 29.16 | σs | −12.11 | −0.92 | 2.22 | 2.07 | 0.96 |
ΔEint,ave | dTM-O,ave | dTM-σ,ave | dσ-O,ave | R2V | R2E | |
---|---|---|---|---|---|---|
Au13 | −0.29 | 2.57 | 2.21 | 0.83 | 0.84 | 0.81 |
Cu13 | −0.47 | 2.19 | 2.06 | 0.43 | 0.85 | 0.95 |
Pt13 | −0.47 | 2.38 | 2.20 | 0.46 | 0.67 1 | 0.82 1 |
Pt7Cu6 | −0.47 2 | 2.30 2 | 2.09 | 0.57 2 | 0.92 2 | 0.65 2 |
Pd13 | −0.45 | 2.34 | 2.15 | 0.82 | 0.58 | 0.25 |
Co13 | −0.470 | 2.15 | 2.10 | 0.61 | n.a. 3 | n.a. 3 |
Rh13 | −0.64 | 2.29 | 2.15 | 0.37 | 0.19 | 0.18 |
Ir13 | −0.59 | 2.41 | 2.28 | 0.45 | 0.28 (0.90) 4 | 0.09 (0.75) 4 |
Ru13 | −0.64 | 2.25 | 2.17 | 0.91 | 0.03 | 0.10 |
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Stenlid, J.H.; Johansson, A.J.; Brinck, T. σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity. Crystals 2017, 7, 222. https://doi.org/10.3390/cryst7070222
Stenlid JH, Johansson AJ, Brinck T. σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity. Crystals. 2017; 7(7):222. https://doi.org/10.3390/cryst7070222
Chicago/Turabian StyleStenlid, Joakim H., Adam Johannes Johansson, and Tore Brinck. 2017. "σ-Holes on Transition Metal Nanoclusters and Their Influence on the Local Lewis Acidity" Crystals 7, no. 7: 222. https://doi.org/10.3390/cryst7070222