Pd doping, conformational, and charge effects on the dichroic response of a monolayer protected Au38(SR)24 nanocluster
| Autor: | Daniele Toffoli, Luca Sementa, Mauro Stener, Alessandro Fortunelli, Oscar Baseggio, Giovanna Fronzoni |
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| Přispěvatelé: | Toffoli, Daniele, Baseggio, Oscar, Fronzoni, Giovanna, Stener, Mauro, Fortunelli, Alessandro, Sementa, Luca |
| Rok vydání: | 2019 |
| Předmět: |
Materials science
TDDFT calculations absorption and CD spectra Ligand Doping General Physics and Astronomy 02 engineering and technology Time-dependent density functional theory 010402 general chemistry 021001 nanoscience & nanotechnology Dichroic glass 01 natural sciences Molecular physics Spectral line 0104 chemical sciences absorption and CD spectra Monolayer TDDFT simulations CD spectra monolayer-protected clusters Physical and Theoretical Chemistry Optical rotation 0210 nano-technology Absorption (electromagnetic radiation) TDDFT calculations |
| Zdroj: | PCCP. Physical chemistry chemical physics 21 (2019): 3585–3596. doi:10.1039/c8cp04107e info:cnr-pdr/source/autori:Toffoli D.; Baseggio O.; Fronzoni G.; Stener M.; Fortunelli A.; Sementa L./titolo:Pd doping, conformational, and charge effects on the dichroic response of a monolayer protected Au 38 (SR) 24 nanocluster/doi:10.1039%2Fc8cp04107e/rivista:PCCP. Physical chemistry chemical physics (Print)/anno:2019/pagina_da:3585/pagina_a:3596/intervallo_pagine:3585–3596/volume:21 |
| ISSN: | 1463-9084 1463-9076 |
| DOI: | 10.1039/c8cp04107e |
| Popis: | TDDFT simulations of the absorption and CD spectra of a Pd 2 Au 36 (SC 2 H 4 Ph) 24 monolayer-protected cluster (MPC) are carried out with the aim of investigating the effects of doping, conformational degrees of freedom of the thiolates' end-groups, and charge states on the optical and dichroic response of a prototypical MPC species. Clear signatures of Pd doping in both absorption and CD spectra are found to be a consequence of the participation of Pd (4d) states in the ligand-based d-band and on the unoccupied MOs of lower energy. Exploration of conformational space points to a much greater sensitivity of optical rotation to the conformation of the end-groups of the organic monolayer compared to absorption. Finally, the effect of charge is mainly seen as a decreased dependence of the dichroic response on conformation. The agreement between the TDDFT predictions and the available experimental data is good, and enables an assignment of absorption and CD bands to specific classes of one-particle excitations. |
| Databáze: | OpenAIRE |
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