Analyzing the vibrational signatures of thiophenol adsorbed on small gold clusters by DFT calculations

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Using density functional theory, we calculate the IR and Raman signatures of the thiophenol (TP) molecule adsorbed on gold clusters by mimicking the different types of adsorption sites, and we analyze these signatures by using advanced tools implemented into the pyvib2 program. First, we follow the evolution of the vibrational normal modes from the isolated TP molecule to those of TP adsorbed on different clusters to highlight the influence of the site of adsorption on the vibrational motions. The use of the overlap matrix between the modes enables mode permutations, mode mixings, and mode splittings to be highlighted, all of which depend not only on the adsorption but also on the type of cluster and its symmetry. Second, the IR and Raman signatures were analyzed by using group coupling matrices and atomic contribution patterns based on the Hug decomposition scheme. Key results include 1) the fact that Raman spectroscopy is more sensitive than IR spectroscopy with respect to the nature of the coordination site, 2) an IR criterion that distinguishes between on-top coordination (onefold coordinated) with respect to the bridge (twofold coordinated) and hexagonal close-packed hollow site coordination (threefold coordinated), and 3) the best agreement to the experimental Raman spectrum with regard to signatures in the 500 to 1200 cm-1 region is obtained for bridged, twofold coordination. Vibrational fingerprint: Using density functional theory, the IR and Raman signatures of thiophenol adsorbed on gold clusters are calculated by mimicking the different types of adsorption sites. The evolution of the vibrational normal modes of isolated TP and TP adsorbed on different clusters is examined, and the IR and Raman signatures are analyzed by using group coupling matrices and atomic contribution patterns.

langue originaleAnglais
Pages (de - à)1633-1645
Nombre de pages13
journalChemPhysChem
Volume14
Numéro de publication8
Les DOIs
étatPublié - 3 juin 2013

Empreinte digitale

Discrete Fourier transforms
Gold
signatures
gold
Adsorption
adsorption
Density functional theory
matrices
density functional theory
Molecules
permutations
Raman spectroscopy
thiophenol
Raman scattering
molecules
Infrared spectroscopy
hollow
Raman spectra
Decomposition
decomposition

Citer ceci

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abstract = "Using density functional theory, we calculate the IR and Raman signatures of the thiophenol (TP) molecule adsorbed on gold clusters by mimicking the different types of adsorption sites, and we analyze these signatures by using advanced tools implemented into the pyvib2 program. First, we follow the evolution of the vibrational normal modes from the isolated TP molecule to those of TP adsorbed on different clusters to highlight the influence of the site of adsorption on the vibrational motions. The use of the overlap matrix between the modes enables mode permutations, mode mixings, and mode splittings to be highlighted, all of which depend not only on the adsorption but also on the type of cluster and its symmetry. Second, the IR and Raman signatures were analyzed by using group coupling matrices and atomic contribution patterns based on the Hug decomposition scheme. Key results include 1) the fact that Raman spectroscopy is more sensitive than IR spectroscopy with respect to the nature of the coordination site, 2) an IR criterion that distinguishes between on-top coordination (onefold coordinated) with respect to the bridge (twofold coordinated) and hexagonal close-packed hollow site coordination (threefold coordinated), and 3) the best agreement to the experimental Raman spectrum with regard to signatures in the 500 to 1200 cm-1 region is obtained for bridged, twofold coordination. Vibrational fingerprint: Using density functional theory, the IR and Raman signatures of thiophenol adsorbed on gold clusters are calculated by mimicking the different types of adsorption sites. The evolution of the vibrational normal modes of isolated TP and TP adsorbed on different clusters is examined, and the IR and Raman signatures are analyzed by using group coupling matrices and atomic contribution patterns.",
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author = "Feugmo, {Conrard Giresse Tetsassi} and Vincent Li{\'e}geois",
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Analyzing the vibrational signatures of thiophenol adsorbed on small gold clusters by DFT calculations. / Feugmo, Conrard Giresse Tetsassi; Liégeois, Vincent.

Dans: ChemPhysChem, Vol 14, Numéro 8, 03.06.2013, p. 1633-1645.

Résultats de recherche: Contribution à un journal/une revueArticle

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T1 - Analyzing the vibrational signatures of thiophenol adsorbed on small gold clusters by DFT calculations

AU - Feugmo, Conrard Giresse Tetsassi

AU - Liégeois, Vincent

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N2 - Using density functional theory, we calculate the IR and Raman signatures of the thiophenol (TP) molecule adsorbed on gold clusters by mimicking the different types of adsorption sites, and we analyze these signatures by using advanced tools implemented into the pyvib2 program. First, we follow the evolution of the vibrational normal modes from the isolated TP molecule to those of TP adsorbed on different clusters to highlight the influence of the site of adsorption on the vibrational motions. The use of the overlap matrix between the modes enables mode permutations, mode mixings, and mode splittings to be highlighted, all of which depend not only on the adsorption but also on the type of cluster and its symmetry. Second, the IR and Raman signatures were analyzed by using group coupling matrices and atomic contribution patterns based on the Hug decomposition scheme. Key results include 1) the fact that Raman spectroscopy is more sensitive than IR spectroscopy with respect to the nature of the coordination site, 2) an IR criterion that distinguishes between on-top coordination (onefold coordinated) with respect to the bridge (twofold coordinated) and hexagonal close-packed hollow site coordination (threefold coordinated), and 3) the best agreement to the experimental Raman spectrum with regard to signatures in the 500 to 1200 cm-1 region is obtained for bridged, twofold coordination. Vibrational fingerprint: Using density functional theory, the IR and Raman signatures of thiophenol adsorbed on gold clusters are calculated by mimicking the different types of adsorption sites. The evolution of the vibrational normal modes of isolated TP and TP adsorbed on different clusters is examined, and the IR and Raman signatures are analyzed by using group coupling matrices and atomic contribution patterns.

AB - Using density functional theory, we calculate the IR and Raman signatures of the thiophenol (TP) molecule adsorbed on gold clusters by mimicking the different types of adsorption sites, and we analyze these signatures by using advanced tools implemented into the pyvib2 program. First, we follow the evolution of the vibrational normal modes from the isolated TP molecule to those of TP adsorbed on different clusters to highlight the influence of the site of adsorption on the vibrational motions. The use of the overlap matrix between the modes enables mode permutations, mode mixings, and mode splittings to be highlighted, all of which depend not only on the adsorption but also on the type of cluster and its symmetry. Second, the IR and Raman signatures were analyzed by using group coupling matrices and atomic contribution patterns based on the Hug decomposition scheme. Key results include 1) the fact that Raman spectroscopy is more sensitive than IR spectroscopy with respect to the nature of the coordination site, 2) an IR criterion that distinguishes between on-top coordination (onefold coordinated) with respect to the bridge (twofold coordinated) and hexagonal close-packed hollow site coordination (threefold coordinated), and 3) the best agreement to the experimental Raman spectrum with regard to signatures in the 500 to 1200 cm-1 region is obtained for bridged, twofold coordination. Vibrational fingerprint: Using density functional theory, the IR and Raman signatures of thiophenol adsorbed on gold clusters are calculated by mimicking the different types of adsorption sites. The evolution of the vibrational normal modes of isolated TP and TP adsorbed on different clusters is examined, and the IR and Raman signatures are analyzed by using group coupling matrices and atomic contribution patterns.

KW - density functional calculations

KW - gold

KW - IR spectroscopy

KW - raman spectroscopy

KW - vibrational spectroscopy

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