The A′1u ← X0+g System of Gold Dimer

James, Andrew M.; Kowalczyk, P.; Simard, Benoît; Pinegar, Jacqueline C.; Morse, Michael D.

doi:10.1006/jmsp.1994.1275

Cited by 49 publications

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“…The predicted bond length and the frequency of the stretching mode of the ground-state Au 2 are 2.535 Å and 171.3 cm −1 , respectively, in good agreement with the experimentally observed values (2.473 Åand 190.9 cm −1 ) [33,34]. NEC analysis shows a slight electron promotion from 5d to 6s in both Au atoms and indicates the participation of the 5d orbital in the bond formation of Au 2 .…”

Section: Au M and Ptau N Clusterssupporting

confidence: 84%

Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes

Chen

Wang

2011

Int J of Quantum Chemistry

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Small homonuclear Au m (m ≤ 5) and bimetallic PtAu n (n ≤ 4) clusters were studied using density functional theory. Both homonuclear and bimetallic clusters tend to form compact two-dimensional structures. All the low-lying Au m clusters have delocalized highest occupied molecular orbitals (HOMOs), whereas all the PtAu n clusters have more localized HOMOs on the Pt atom. The localized HOMO makes the PtAu n clusters more regioselective toward electrophilic reactions than the Au m clusters. Adsorptions of N 2 and O 2 onto these metal clusters were further studied. In N 2 adsorption, the metal clusters donate their electrons primarily to the σ * orbitals of N 2 to form end-on complexes preferably. In O 2 adsorption, complicated π orbital interactions between the cluster and O 2 dominate to form side-on complexes with relatively larger binding energies.

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Section: Au M and Ptau N Clusterssupporting

confidence: 84%

Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes

Chen

Wang

2011

Int J of Quantum Chemistry

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“…43 The cohesive energies of Au 2 and Au 3 are 24.32 and 24.63 kcal mol À1 , which is also in agreement with the experimental results (26.82 and 29.23 kcal mol À1 ), respectively. [44][45][46] For the Au 3 cluster, the acute triangle structure is higher than the obtuse triangle structure about 1.67 kcal mol À1 , which is in line with results obtained at the various functionals and basis sets. 31,47 As shown in Fig.…”

Section: Resultssupporting

confidence: 89%

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

et al. 2016

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A detailed reaction mechanism of the triatomic gold cluster-catalyzed cycloisomerization of u-alkynylfuran was systemically investigated via density functional theory at the TPSSh/def2-TZVP level. The computational results indicated that the 5-exo Friedel-Crafts-type mechanism is the most favorable mechanism to form the phenol derivatives. The strong interaction between the gold and vinyl fragments in the Friedel-Crafts adduct is essential for the priority of the 5-exo Friedel-Crafts-type mechanism. Then, the 5-exo Friedel-Crafts-type mechanism on the various planar gold clusters (Au 4-10 ) was studied to clarify the size-effects of the planar gold clusters catalyzed u-alkynylfuran cycloisomerization. The appropriate interactions between the alkyne group in the substrate and gold clusters play a key role for the 5-exo cyclization step. The energy barriers of the ring-closure of the dienone carbene-gold intermediate step show an interesting "odd-even" behavior respective to the number of gold atoms. The Au 3 and Au 4 clusters are the most active catalysts for the u-alkynylfuran cycloisomerization to the phenol derivative. We also found that the active catalyst of the u-alkynylfuran cycloisomerization catalyzed by the gold(I) complexes should be the gold(0) complexes of the in situ generation. The catalytic activity of the gold(0) complex is comparable with that of the planar gold clusters. These findings may guide the rational design of highly active gold catalysts for the u-alkynylfuran cycloisomerization to phenol derivatives. † Electronic supplementary information (ESI) available: Fig. S1-S15, Tables S1-S9, details of the energy decomposition analysis, and the Cartesian coordinates, single point electronic energies (in the gas phase and acetonitrile), zero-point, and free energy correction for all of the stationary points and imaginary frequencies of transition structures. See Scheme 2 Different transition metal complex-catalyzed-u-alkynylfurans cycloisomerizations.Scheme 3 Proposed mechanism for the gold-catalyzed phenol synthesis.

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“…44 We fitted the observed vibrational spacings for both the anionic and neutral ground state of Au 2 to an anharmonic oscillator described by the Morse potential and obtained a relatively accurate harmonic vibrational frequency and anharmonicity for Au 2 − , as given in Table I along with literature values. Furthermore, using the accurate EA value measured in this work together with a redefinition of the dissociation energy for Au 2 by Morse and coworkers, 31 we obtained a more accurate dissociation en-ergy for the ground state of Au 2 − as 1.937 ± 0.005 eV (Table I).…”

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confidence: 64%

“…Au 2 − was a) E-mail: Lai-Sheng_Wang@brown.edu selected because of its well-known spectroscopy. 7,[27][28][29][30][31][32][33] In particular, a vibrationally resolved PES spectrum of Au 2 − was first reported by Lineberger and co-workers using a hemispherical electron analyzer at a resolution of ∼6 meV and a vibrational temperature of 350 ± 25 K. 28 Gantefor and coworkers reported a ZEKE spectrum of Au 2 − in the photon energy range of 1.85 to 2.025 eV at a spectral resolution of 1.5 meV and a vibrational temperature of 165 ± 30 K. 7 In the current work, we report photoelectron images of Au 2 − in the photon energy range of 1.8470 eV (671.28 nm) to 2.8000 eV (442.80 nm) at a vibrational temperature of 175 ± 25 K and a kinetic energy resolution of 2.8 cm −1 for slow electrons.…”

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confidence: 99%

High resolution photoelectron imaging of Au2−

León

Yang

Wang

2013

The Journal of Chemical Physics

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We report high resolution photoelectron spectra of Au2(-) using a newly built photoelectron imaging apparatus. Vibrationally resolved photoelectron images are obtained for the ground state detachment transition of Au2(-) at various photon energies (442.80-670.18 nm) at a resolution of 3 cm(-1) for low energy electrons. Franck-Condon simulations yield the vibrational temperature of Au2(-) and the high resolution data yield accurate spectroscopic constants for the ground states of Au2 and Au2(-). The electron affinity of Au2 is measured to be 1.9393 ± 0.0006 eV. A more precise value for the Au2(-) dissociation energy is also obtained as 1.937 ± 0.005 eV.

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The A′1u ← X0+g System of Gold Dimer

Cited by 49 publications

References 0 publications

Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes

Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

High resolution photoelectron imaging of Au2−

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The A′1u ← X0+g System of Gold Dimer

Cited by 49 publications

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Theoretical studies of Aum and PtAun clusters and their N2 and O2 adsorption complexes

Theoretical studies of Aum and PtAun clusters and their N2 and O2 adsorption complexes

DFT insights into the cycloisomerization of ω-alkynylfuran catalyzed by planar gold clusters: mechanism and selectivity, as compared to Au(i)-catalysis

High resolution photoelectron imaging of Au2−

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Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes

Theoretical studies of Au_m and PtAu_n clusters and their N₂ and O₂ adsorption complexes