The experimental characterization of Cl@Si20 endohedral clusters, featuring different ligands such as Cl@Si20H20− (1) Cl@Si20H12Cl8− (2), and Cl@Si20Cl20− (3), provides insight into the variable ...encapsulation environment for chloride anions. The favorable formation of such species enables the evaluation of the encapsulation nature and the role of the inner anion in the rigidity of the overall cluster. Our results show a sizable interaction which increases as −66.7, −100.8, and −130.3 kcal mol−1 from 1 to 3, respectively, featuring electrostatic character. The orbital interaction involves 3p-Cl → Si20X20 and 3s-Cl → Si20X20 charge transfer channels and a slight contribution from London dispersion-type interactions. These results show that the inner bonding environment can be modified by the choice of exobonded ligands. Moreover, 29Si-NMR parameters are depicted in terms of the chemical shift anisotropy (CSA), leading to a strong variation of the three principal tensor components (δ11, δ22, δ33), unraveling the origin of the experimental 29Si-NMR chemical shift (δiso) differences along the given series. Thus, the Si20 cage is a useful template to further evaluate different environments for encapsulating atomic species.
The experimental characterization of Cl@Si
20
endohedral clusters, featuring different ligands such as Cl@Si
20
H
20
−
(
1
) Cl@Si
20
H
12
Cl
8
−
(
2
), and Cl@Si
20
Cl
20
−
(
3
), provides ...insight into the variable encapsulation environment for chloride anions. The favorable formation of such species enables the evaluation of the encapsulation nature and the role of the inner anion in the rigidity of the overall cluster. Our results show a sizable interaction which increases as −66.7, −100.8, and −130.3 kcal mol
−1
from
1
to
3
, respectively, featuring electrostatic character. The orbital interaction involves 3p-Cl → Si
20
X
20
and 3s-Cl → Si
20
X
20
charge transfer channels and a slight contribution from London dispersion-type interactions. These results show that the inner bonding environment can be modified by the choice of exobonded ligands. Moreover,
29
Si-NMR parameters are depicted in terms of the chemical shift anisotropy (CSA), leading to a strong variation of the three principal tensor components (
δ
11
,
δ
22
,
δ
33
), unraveling the origin of the experimental
29
Si-NMR chemical shift (
δ
iso
) differences along the given series. Thus, the Si
20
cage is a useful template to further evaluate different environments for encapsulating atomic species.
Molecular scale Roman dodecahedrons as anion cages. The nature of the interaction and
29
Si-NMR-properties reveal the tailorable capabilities of the Si
20
towards further modification as three-dimensional hosts.
The hydrogen storage properties of Ti‐doped Bn (n=3−12) clusters are investigated by using the “diatomic deposition method” with further evaluation by density functional theory computations. The ...results show that TiBn (n=7−9) clusters possess the ability to storage up to four H2 molecules, reaching a mass fraction of 6.12%. Further, the hydrogen release temperature is analyzed by molecular dynamics simulations with a variable temperature. It turns out that the TiB7 and TiB9 clusters release the H2 molecules at T ≲ 700 K, while TiB8 requires higher temperature due to stronger interactions with the H2 molecules, confirmed by the electronic density of states. The size‐dependent properties and odd–even nuclearity on the clusters can be useful for applications with controlled temperature. These results serve for further design of novel materials with reversible and controlled hydrogen storage properties based on TiB7/TiB9 motifs. Additionally, new lower‐energy isomers for TiB4 and TiB9 clusters were found within the accuracy of the all‐electron triple‐ζ Slater slater type orbital (STO)‐Triple‐zeta basis set(TZP) basis set.
The diatomic deposition method is applied for investigating the hydrogen storage properties of Ti‐doped Bn (n = 3–10) clusters. The hydrogen release temperature is analyzed by molecular dynamics simulation. Depending on the number of boron atoms, the release temperature occurs around T = 700 K for TiB7 and TiB9, while TiB8 requires higher temperature due to stronger interactions with the H2 molecules.
Abstract
The structural evolution of Ti
n
() clusters has been investigated by using the systematic cluster growth method together with the many‐body Gupta potential. The lowest energy structures are ...further refined by using density functional theory computations within the accuracy of the Perdew‐Burke‐Ernzerhof (PBE) exchange‐correlation functional and a plane‐wave basis set. Using this approach, the structures and stability trends of Ti
n
clusters in the size range previously reported, are reproduced. New clusters with enhanced stability are found for , 38, 41, 43, 46, 48, 50, 53, 55, and 58 sizes. Tightly packed structures dominate principally for these clusters in which the shape of the structures can be understood based on the encapsulated motif. The geometries of the clusters from Ti
33
up to Ti
60
adopt oblate forms which is in contrast to the smaller clusters. The vertical ionization potential (vIP) and vertical electron affinity (vEA) curves show a step behavior depending of the size range for , while the chemical hardness decreases monotonically with the size, which is consistent with the d‐band center parameter. In contrast to previous reports, for it is found that a distorted Mackay icosahedron is more stable than the regular one. The theoretical electronic properties for the most stable isomers of Ti
n
clusters are in good agreement with the available experimental data.
Correction for 'Structure effects of Pt
15
clusters for the oxygen reduction reaction: first-principles calculations' by Peter L. Rodríguez-Kessler
et al.
,
Phys. Chem. Chem. Phys.
, 2023,
...https://doi.org/10.1039/d2cp05188e
.
Correction for ‘Structure effects of Pt15 clusters for the oxygen reduction reaction: first-principles calculations’ by Peter L. Rodríguez-Kessler et al., Phys. Chem. Chem. Phys., 2023, ...https://doi.org/10.1039/d2cp05188e.
In the present work, the lowest energy structures and electronic properties of Pt
15
clusters are investigated using molecular dynamics simulations. The results showed that the most stable ...configuration is a capped pyramidal structure, which is 0.8 kal mol
−1
lower in energy than a layered structure previously reported V. Kumar and Y. Kawazoe, Evolution of Atomic and Electronic Structure of Pt Clusters: Planar, Layered, Pyramidal, Cage, Cubic, and Octahedral Growth,
Phys. Rev. B: Condens. Matter Mater. Phys.
, 2008,
77
, 205418.. The result is further confirmed by using both the PW91/cc-pVDZ-PP and PBE/PW approaches including the other representative isomers for Pt
15
. Due to the interesting structure arrangements found, we have investigated the catalytic activities for the oxygen reduction reaction. We found that the most stable Pt
15
clusters are plausible catalyts for the ORR according to their interaction with oxygen species, which is consistent with experiments of Pt clusters with atomicity below 20. The results of the structure, electronic, adsorption and vibrational properties of the clusters are provided.
In the present work, the lowest energy structures and electronic properties of Pt
15
clusters are investigated using first-principles calculations. The catalytic activity for the oxygen reduction reaction is analyzed and discussed.
Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold–phosphine M13(dppe)6 cluster, as ...a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1–3 nm size range, via relativistic DFT calculations. Different charge states involving 8- and 10-cluster electron (ce) species with a 1S21P6 and 1S21P61D2 configuration, leading to structural modification in the Au species between Au13(dppm)65+ and Au13(dppm)63+, respectively. Furthermore, this structural distortion of the M13 core is found to occur to a lower degree for the calculated Ag and Cu counterparts. Interestingly, optical properties exhibit similar main patterns along with the series, inducing a blue-shift for silver and copper, in comparison to the gold parent cluster. For 10-ce species, the main features of 8-ce are retained with the appearance of several weak transitions in the range. The ligand–core interaction is enhanced for gold counterparts and decreased for lighter counterparts resulting in the Au > Cu > Ag trend for the interaction stabilization. Hence, the Ag and Cu counterparts of the Au13(dppm)6 cluster appear as useful alternatives, which can be further explored towards different cluster alternatives for building blocks for nanostructured materials.
Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold-phosphine M
13
(dppe)
6
cluster, ...as a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1-3 nm size range,
via
relativistic DFT calculations. Different charge states involving 8- and 10-cluster electron (
ce
) species with a 1S
2
1P
6
and 1S
2
1P
6
1D
2
configuration, leading to structural modification in the Au species between Au
13
(dppm)
6
5+
and Au
13
(dppm)
6
3+
, respectively. Furthermore, this structural distortion of the M
13
core is found to occur to a lower degree for the calculated Ag and Cu counterparts. Interestingly, optical properties exhibit similar main patterns along with the series, inducing a blue-shift for silver and copper, in comparison to the gold parent cluster. For 10-
ce
species, the main features of 8-
ce
are retained with the appearance of several weak transitions in the range. The ligand-core interaction is enhanced for gold counterparts and decreased for lighter counterparts resulting in the Au > Cu > Ag trend for the interaction stabilization. Hence, the Ag and Cu counterparts of the Au
13
(dppm)
6
cluster appear as useful alternatives, which can be further explored towards different cluster alternatives for building blocks for nanostructured materials.
Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range.
Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold–phosphine M 13 (dppe) 6 cluster, ...as a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1–3 nm size range, via relativistic DFT calculations. Different charge states involving 8- and 10-cluster electron ( ce ) species with a 1S 2 1P 6 and 1S 2 1P 6 1D 2 configuration, leading to structural modification in the Au species between Au 13 (dppm) 6 5+ and Au 13 (dppm) 6 3+ , respectively. Furthermore, this structural distortion of the M 13 core is found to occur to a lower degree for the calculated Ag and Cu counterparts. Interestingly, optical properties exhibit similar main patterns along with the series, inducing a blue-shift for silver and copper, in comparison to the gold parent cluster. For 10- ce species, the main features of 8- ce are retained with the appearance of several weak transitions in the range. The ligand–core interaction is enhanced for gold counterparts and decreased for lighter counterparts resulting in the Au > Cu > Ag trend for the interaction stabilization. Hence, the Ag and Cu counterparts of the Au 13 (dppm) 6 cluster appear as useful alternatives, which can be further explored towards different cluster alternatives for building blocks for nanostructured materials.
