Characterization of optical spectra of interacting systems: Application to oxide‐supported metal clusters

Huix‐Rotllant, Miquel; Deka, Ajanta; Matveev, Alexei V.; Bosko, Sergey; Moskaleva, Lyudmila V.; Rösch, Notker

doi:10.1002/qua.21853

Cited by 3 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These authors also carried out molecular dynamics (MD) simulations in the excited electronic states to unravel the relaxation mechanism and to propose that dimers and tetramers are good candidates for emissive centers whereas larger supported Ag 8 and Au 8 are unlikely to fluoresce. To interpret the optical spectra of metal clusters at oxide surfaces, Huix-Rotllant et al 454 proposed a new strategy based on the combined use of natural transition orbital and fragment molecular orbital analyses. These authors applied this methodology to the case of coinage metal dimers supported also on the F s center of MgO, represented by an embedded cluster model.…”

Section: Metal Atoms and Metal Clustersmentioning

confidence: 99%

Theoretical Approaches to Excited-State-Related Phenomena in Oxide Surfaces

2012

View full text Add to dashboard Cite

Section: Metal Atoms and Metal Clustersmentioning

confidence: 99%

Theoretical Approaches to Excited-State-Related Phenomena in Oxide Surfaces

2012

View full text Add to dashboard Cite

“…41 More recently, Wang et al performed a detailed study of Cu 2 within the time-dependent density functional theory (TDDFT) using the hybrid B3LYP functional. 42 Optical properties of free and MgO(100)-supported Cu n clusters have been investigated by Del Vitto et al 43 for n = 1, 2, 4 using B3LYP-TDDFT and complete active space second-order perturbation theory (CASPT2); by Bosko et al 44 for n = 1 − 2, and by Huix-Rotllant et al 45 for n = 2 using TDDFT with the Becke and Perdew (BP86) functional. Recently, Zhou and Zeng performed a TDDFT study of Cu n (n = 3 − 9) clusters using the Amsterdam Density Functional code.…”

Section: Introductionmentioning

confidence: 99%

First-principles absorption spectra of Cun(n=2–20) clusters

et al. 2011

View full text Add to dashboard Cite

Optical absorption spectra for the computed ground state structures of copper clusters (Cun, n = 2 − 20) are investigated from first principles using time-dependent density functional theory in the adiabatic local density approximation (TDLDA). The results are compared with available experimental data, existing calculations, and with results from our previous computations on silver and gold clusters. The main effects of d electrons on the absorption spectra, quenching the oscillator strengths and getting directly involved in low-energy excitations, increase in going from Agn to Aun to Cun due to the increase in the hybridization of the occupied, yet shallow, d orbitals and the partially occupied s orbitals. We predict that while Cu nanoparticles of spherical or moderately ellipsoidal shape do not exhibit Mie (surface plasmon) resonances unlike the case for Ag and Au, extremely prolate or oblate Cu nanoparticles with eccentricities near unity should give rise to Mie resonances in the lower end of the visible range and in the infra-red. This tunable resonance predicted by the classical Mie-Gans theory is reproduced with remarkable accuracy by our TDLDA computations on hypothetical Cu clusters in the form of zigzag chains with as few as 6 to 20 atoms.

show abstract

“…The optical properties of supported noble‐metal clusters have been scarcely investigated 27, 32–39. The adsorption and optical properties of small noble‐metal clusters Cu 1,2,4 /Ag 1,2 /Au 1,2 supported at MgO 34, 35, 39 as well as of gold Au 1,2 clusters at SiO 2 36, 37 have been previously theoretically investigated. Schaffner et al 33 recorded absorption spectra of supported silver clusters at MgO/W thin film employing the electron energy loss spectroscopy (EELS), and found rich absorption features within the MgO band gap.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of structural and optical properties of small silver and gold clusters at defect centers of MgO

Bürgel

Mitrić

Bonačić‐Koutecký

2010

Physica Status Solidi (b)

View full text Add to dashboard Cite

In this contribution we present the structural and optical properties of small noble-metal clusters at the F S -center defect of the MgO (100) support. We focus on comparing absorption and emission properties of supported silver and gold clusters. It will be shown that the leading absorption features in the low energy regime are similar for supported silver and gold clusters of the same size, in spite of the direct involvement of d electrons from Au atoms due to strong relativistic effects. Molecular dynamics (MD) simulations in the excited electronic states allow us to unravel relaxation mechanism and to propose the smallest noble-metal clusters at the F S -center defect, Ag 2,4 @F 5c and Au 2,4 @F 5c , as good candidates for emissive centers. In contrast, larger supported Ag 8 @F 5c and Au 8 @F 5c clusters are unlikely to fluoresce. 1 Introduction Small noble-metal clusters in different environments exhibit intense optical transitions in the ultra-violet (UV) or in the visible regime and, in contrast to the bulk materials, they fluoresce. Discovery of fluorescent silver particles [1-6] opened new perspectives for different applications which stimulated many researchers to pursue the development of new materials for optical data storage [3,[7][8][9], optoelectronic devices [8,10], and biosensing [11,12]. Gold clusters also exhibit strong absorption and emissive properties in the nano-meter size regime [13][14][15][16][17][18][19][20][21][22] which allows potential application as optical materials [14,22], photocatalysts [15], and biosensors [16,23]. Actually, quantum confinement of electrons is responsible for these fascinating properties. Small noble-metal clusters with discrete energy levels exhibit strong fluorescence in rare gas matrices [1, 2, 4-6, 13, 17, 24], helium droplets [25], at surfaces [3, 7-9, 26, 27], or in bio-environment [16, 19-21, 28, 29]. Their size dependent effects are particularly pronounced in the nonscalable size regime in which each atom counts [30,31] because addition of single atom influences strongly cluster structures, absorption patterns, and the nature of the excited electronic states.

show abstract

Characterization of optical spectra of interacting systems: Application to oxide‐supported metal clusters

Cited by 3 publications

References 42 publications

Theoretical Approaches to Excited-State-Related Phenomena in Oxide Surfaces

Theoretical Approaches to Excited-State-Related Phenomena in Oxide Surfaces

First-principles absorption spectra of Cun(n=2–20) clusters

Theoretical study of structural and optical properties of small silver and gold clusters at defect centers of MgO

Contact Info

Product

Resources

About