Methanol C–O Bond Activation by Free Gold Clusters Probed via Infrared Photodissociation Spectroscopy

2019 ◽  
Vol 233 (6) ◽  
pp. 865-880 ◽  
Author(s):  
Sandra M. Lang ◽  
Thorsten M. Bernhardt ◽  
Joost M. Bakker ◽  
Bokwon Yoon ◽  
Uzi Landman
Keyword(s):  
Density Functional ◽  
Bond Activation ◽  
Spectral Shift ◽  
Gold Clusters ◽  
Size Number ◽  
Free Gold ◽  
Theoretical Investigations ◽  
Multiphoton Dissociation ◽  
Stretch Mode ◽  
Cationic Gold

Abstract The activation of methanol (CD3OD and CD3OH) by small cationic gold clusters has been investigated via infrared multiphoton dissociation (IR-MPD) spectroscopy in the 615–1760 cm−1 frequency range. The C–O stretch mode around 925 cm−1 and a coupled CD3 deformation/C–O stretch mode around 1085 cm−1 are identified to be sensitive to the interaction between methanol and the gold clusters, whereas all other modes in the investigated spectral region remain unaffected. Based on the spectral shift of these modes, the largest C–O bond activation is observed for the mono-gold Au(CD3OD)+ cluster. This activation decreases with increasing the cluster size (number of gold atoms) and the number of adsorbed methanol molecules. Supporting density functional theory (DFT) calculations reveal that the C–O bond activation is caused by a methanol to gold charge donation, whereas the C–D and O–D bonds are not significantly activated by this process. The results are discussed with respect to previous experimental and theoretical investigations of neutral and cationic gold-methanol complexes focusing on the C–O stretch mode.

The structures of cationic gold clusters probed by far-infrared spectroscopy

2020 ◽  
Vol 22 (20) ◽  
pp. 11572-11577 ◽  
Author(s):  
Piero Ferrari ◽  
Gao-Lei Hou ◽  
Olga V. Lushchikova ◽  
Florent Calvo ◽  
Joost M. Bakker ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Infrared Spectroscopy ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Far Infrared ◽  
Gold Clusters ◽  
Far Infrared Spectroscopy ◽  
Functional Theory ◽  
Infrared Multiple Photon Dissociation ◽  
Cationic Gold

Far-infrared multiple photon dissociation spectroscopy is used in combination with density functional theory calculations to determine the structures of isolated Aun+ (n ≤ 9) clusters.

scholarly journals Selective C H bond activation of ethane by free gold clusters

2019 ◽  
Vol 435 ◽  
pp. 241-250 ◽  
Author(s):  
Sandra M. Lang ◽  
Thorsten M. Bernhardt ◽  
Joost M. Bakker ◽  
Bokwon Yoon ◽  
Uzi Landman
Keyword(s):  
Bond Activation ◽  
Gold Clusters ◽  
Free Gold

Mechanistic insights into α-branched amines formation with pivalic acid assisted C−H bond activation catalysed by Cp*Rh complexes

2021 ◽  
Author(s):  
Rongrong Li ◽  
Xinzheng Yang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Bond Activation ◽  
Pivalic Acid ◽  
Activation Mechanism ◽  
Functional Theory ◽  
Density Functional Theory Computations ◽  
Reaction Energies

Density functional theory computations revealed a pivalic acid assisted C−H bond activation mechanism for rhodium catalyzed formation of α-branched amines with C−C and C−N bond couplings. The reaction energies of...

Theoretical Investigations on Mechanical Stability and Electronic Structure of NbN under Pressures

2011 ◽  
Vol 90-93 ◽  
pp. 1264-1271
Author(s):  
Xiao Feng Li ◽  
Jun Yi Du
Keyword(s):  
Debye Temperature ◽  
Density Functional ◽  
Mechanical Stability ◽  
Structural Parameters ◽  
Theoretical Data ◽  
Hexagonal Structure ◽  
Functional Theory ◽  
Theoretical Investigations ◽  
Crystallographic Structures ◽  
Good Agreement

The ground structure, elastic and electronic properties of several phases of NbN are determined based on ab initio total-energy calculations within the framework of density functional theory. Among the five crystallographic structures that have been investigated, the hexagonal phases have been found to be more stable than the cubic ones. The calculated equilibrium structural parameters are in good agreement with the available experimental results. The elastic constants of five structures in NbN are calculated, which are in consistent with the obtained theoretical and experimental data. The corresponding Debye temperature and elastic ansitropies are also obtained. The Debye temperature of NbN in various structures consistent with available experimental and theoretical data, in which the Debye temperature of δ-NbN is highest. The anisotropies of ZB-NbN, NaCl-NbN, CsCl-NbN gradually increases. For hexagonal structure, the anisotropies of ε-NbN are stronger than that of δ-NbN. The electronic structures of NbN under pressure are investigated. It is found that NbN have metallization and the hybridizations of atoms in NbN under pressure become stronger.

Cationic gold clusters ligated with differently substituted phosphines: effect of substitution on ligand reactivity and binding

2015 ◽  
Vol 17 (22) ◽  
pp. 14636-14646 ◽  
Author(s):  
Grant E. Johnson ◽  
Astrid Olivares ◽  
David Hill ◽  
Julia Laskin
Keyword(s):  
Ligand Binding ◽  
Lone Pair ◽  
Gold Clusters ◽  
Binding Energies ◽  
Phosphine Ligands ◽  
Strongly Correlated ◽  
P Loss ◽  
Ligand Reactivity ◽  
Cationic Gold

Loss of substituted phosphine ligands is strongly correlated with the electron donating ability of the phosphorous lone pair. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3 < PPh2Cy < PPhCy2 < PCy3.

Estimating the adsorption energy of element 113 on a gold surface

Open Physics ◽  
2013 ◽  
Vol 11 (11) ◽  
Author(s):  
Alexander Rusakov ◽  
Yuriy Demidov ◽  
Andréi Zaitsevskii
Keyword(s):  
Adsorption Energy ◽  
Cluster Size ◽  
Density Functional ◽  
Gold Surface ◽  
Gold Clusters ◽  
Basis Sets ◽  
Energy Estimates ◽  
First Principle ◽  
Gaussian Basis Sets ◽  
Functional Theory

AbstractWe report first-principle based studies of element 113 (E113) interactions with gold aimed primarily at estimating the adsorption energy in thermochromatographic experiments. The electronic structure of E113-Aun systems was treated within the accurate shape-consistent small core relativistic pseudopotential framework at the level of non-collinear relativistic density functional theory (RDFT) with specially optimised Gaussian basis sets. We used gold clusters with up to 58 atoms to simulate the adsorption site on the stable Au(111) surface. Stabilization of the E113-Aun binding energy and the net Bader charge of E113 and the neighboring Au atoms with respect to n indicated the cluster size used was appropriate. The resulting adsorption energy estimates lie within the 1.0–1.2 eV range, substantially lower than previously reported values.

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