TY - JOUR

T1 - Symmetry lowering by cage doping in spherical superatoms

T2 - Evaluation of electronic and optical properties of 18-electron W@Au12Ptn (n = 0-4) superatomic clusters from relativistic DFT calculations

AU - Gam, Franck

AU - Arratia-Perez, Ramiro

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Muñoz-Castro, Alvaro

N1 - Funding Information:
The authors thank the financial support from FONDECYT 1180683. F.G. thanks the Région Bretagne (ARED NANOCLU) and the Universidad Andrés Bello for a joint PhD studentship. Part of the calculations was carried out at the GENCI-CINES and GENCI-IDRISS French national computer centers, which are acknowledged for computational resources (grant a0010807367). This research has been performed as part of the Chilean-French International Associated Laboratory for “Multifunctional Molecules and Materials” (LIA M3 - CNRS N°1027).

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Attempts to expand the versatility of well defined clusters are a relevant issue in the design of building blocks for functional nanostructures. Here, we investigate the plausible formation of related structures from the emblematic highly symmetrical 18-e [W@Au12] cluster. The calculated [W@Au12Ptn] series, with n = 0, 1, 2, 3, and 4, show cohesion energies, HOMO-LUMO gap, adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs), indicating a relative stability to the parent cluster [W@Au12] experimentally characterized, where clusters with n = 1 and n = 4 are suggested as the most stable with respect to oxidation. The resulting symmetry lowering away from the high icosahedral symmetry upon adding Pt atoms induces a sizable splitting of the frontiers shells, which in turn effectively modify the properties of the calculated clusters, as observed from calculated optical properties. The estimated absorption spectra show an interesting broadening effect of the absorption peaks, which appears as a useful approach for further design of broad black absorbers, which are able to absorb light in a wider range, with potential capabilities to enhance the efficiency of thin film solar cells and photocatalysis processes, among other applications.

AB - Attempts to expand the versatility of well defined clusters are a relevant issue in the design of building blocks for functional nanostructures. Here, we investigate the plausible formation of related structures from the emblematic highly symmetrical 18-e [W@Au12] cluster. The calculated [W@Au12Ptn] series, with n = 0, 1, 2, 3, and 4, show cohesion energies, HOMO-LUMO gap, adiabatic electron affinities (AEAs) and adiabatic ionization potentials (AIPs), indicating a relative stability to the parent cluster [W@Au12] experimentally characterized, where clusters with n = 1 and n = 4 are suggested as the most stable with respect to oxidation. The resulting symmetry lowering away from the high icosahedral symmetry upon adding Pt atoms induces a sizable splitting of the frontiers shells, which in turn effectively modify the properties of the calculated clusters, as observed from calculated optical properties. The estimated absorption spectra show an interesting broadening effect of the absorption peaks, which appears as a useful approach for further design of broad black absorbers, which are able to absorb light in a wider range, with potential capabilities to enhance the efficiency of thin film solar cells and photocatalysis processes, among other applications.

KW - endohedral

KW - gold

KW - heteroatomic

KW - platinum

KW - superatoms

UR - http://www.scopus.com/inward/record.url?scp=85056729236&partnerID=8YFLogxK

U2 - 10.1002/qua.25827

DO - 10.1002/qua.25827

M3 - Article

AN - SCOPUS:85056729236

SN - 0020-7608

VL - 119

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

IS - 6

M1 - e25827

ER -