### Abstract

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@Au_{12}] cluster. The calculated [W@Au_{12}Pt_{n}] 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@Au_{12}] 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.

Original language | English |
---|---|

Article number | e25827 |

Journal | International Journal of Quantum Chemistry |

DOIs | |

Publication status | Accepted/In press - 1 Jan 2018 |

### Fingerprint

### Keywords

- endohedral
- gold
- heteroatomic
- platinum
- superatoms

### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics
- Condensed Matter Physics
- Physical and Theoretical Chemistry

### Cite this

_{12}Pt

_{n}(n = 0-4) superatomic clusters from relativistic DFT calculations.

*International Journal of Quantum Chemistry*, [e25827]. https://doi.org/10.1002/qua.25827

}

_{12}Pt

_{n}(n = 0-4) superatomic clusters from relativistic DFT calculations',

*International Journal of Quantum Chemistry*. https://doi.org/10.1002/qua.25827

**Symmetry lowering by cage doping in spherical superatoms : Evaluation of electronic and optical properties of 18-electron W@Au _{12}Pt_{n} (n = 0-4) superatomic clusters from relativistic DFT calculations.** / Gam, Franck; Arratia-Perez, Ramiro; Kahlal, Samia; Saillard, Jean Yves; Muñoz-Castro, Alvaro.

Research output: Contribution to journal › Article

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

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

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

M1 - e25827

ER -

_{12}Pt

_{n}(n = 0-4) superatomic clusters from relativistic DFT calculations. International Journal of Quantum Chemistry. 2018 Jan 1. e25827. https://doi.org/10.1002/qua.25827