Stability and dissociation pathways of doped Au<sub>n</sub>X<sup>+</sup>clusters (X = Y, Er, Nb)

Veldeman, Nele; Janssens, Ewald; Hansen, Klavs; Haeck, Jorg De; Silverans, Roger; Lievens, Peter

doi:10.1039/b705920e

Cited by 41 publications

(55 citation statements)

References 57 publications

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“…To use the theoretical results of the evaporative ensemble outlined hereafter (see references [21,22] for more details), some important assumptions have to be made. First, each cluster in the ensemble must have undergone at least one evaporation.…”

Section: Methodsmentioning

confidence: 99%

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Höltzl

Veldeman

Haeck

et al. 2009

Chemistry A European J

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Size matters! The electronic structure and size-dependent stability of neutral and cationic scandium-doped copper clusters have been investigated by mass spectrometric studies (for the cations) and also quantum chemical computations. The proposed reaction paths ultimately lead to the most stable Frank-Kasper-shaped Cu(16)Sc(+) cluster (shown here), which could be the germ of a new crystallization process.Electronic structure and size-dependent stability of scandium-doped copper cluster cations, Cu(n)Sc(+), were investigated by using a dual-target dual-laser vaporization production scheme followed by mass spectrometric studies and also quantum chemical computations in the density functional theory framework. The neutral species also were studied by using computational methods. Enhanced abundances and dissociation energies were measured in the case of Cu(n)Sc(+) for n=4, 6, 8, 10 and 16, the last of these identified as being extraordinary stable. Neutral clusters are stable with n=5, 7, 9 and 15, which are isoelectronic with respect to the number of the valence s electrons with the stable cationic clusters; hence a simple electron count determines cluster properties to a great extent. The Cu(17)Sc cluster was found to be a superatomic molecule, containing Cu(16)Sc(+) and Cu(-) units; however, the charge separation is not as pronounced as in the case of CuLi. Cu(15)Sc was found to be a stable cluster with a large dissociation energy and a closed electronic structure; hence this can be regarded as a superatom, analogous to the noble gases. The main factors determining the growth patterns of these clusters are the central position of the scandium atom and the successive filling of the shell orbitals. For smaller clusters, the reaction paths appear to diverge yielding various products; however all paths ultimately lead to the most stable Frank-Kasper shaped Cu(16)Sc cluster, which in turn can be the germ of the crystallization process.

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Section: Methodsmentioning

confidence: 99%

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Höltzl

Veldeman

Haeck

et al. 2009

Chemistry A European J

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“…The absorption of multiple photons leads to internal heating of the cluster and subsequent rapid evaporation of atoms with the tendency to terminate at cluster sizes with an enhanced stability relative to adjacent sizes [26,27]. The photofragments are then mass-analyzed in the RTOF.…”

Section: Methodsmentioning

confidence: 99%

Cage Structure Formation of Singly Doped Aluminum Cluster Cations Al_nTM⁺(TM= Ti, V, Cr)

Lang

Claes

Neukermans

et al. 2011

J. Am. Soc. Mass Spectrom.

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Structural information on free transition metal doped aluminum clusters, Al n TM + (TM=Ti, V, Cr), was obtained by studying their ability for argon physisorption. Systematic size (n=5 -35) and temperature (T=145 -300 K) dependent investigations reveal that bare Al n + clusters are inert toward argon, while Al n TM + clusters attach one argon atom up to a critical cluster size. This size is interpreted as the geometrical transition from surface-located dopant atoms to endohedrally doped aluminum clusters with the transition metal atom residing in an aluminum cage. The critical size, n crit , is found to be surprisingly large, namely n crit =16 and n crit =19 -21 for TM=V, Cr, and TM=Ti, respectively. Experimental cluster-argon bond dissociation energies have been derived as function of cluster size from equilibrium mass spectra and are in the 0.1-0.3 eV range.

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“…8,10 Furthermore, photofragmentation studies on a large variety of transition metal doped gold cluster cations provided experimental evidence for dopant induced changes in the electronic shell structure and the number of delocalized electrons. 11 Modification of the geometric and electronic structure upon doping is also reflected in a) Present address: Institute of Surface Chemistry and Catalysis, University of Ulm, 89069 Ulm, Germany. b) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Copper doping of small gold cluster cations: Influence on geometric and electronic structure

Lang

Claes

Cuong

et al. 2011

The Journal of Chemical Physics

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Analytical approach for the excited-state Hessian in time-dependent density functional theory: Formalism, implementation, and performance J. Chem. Phys. 135, 184111 (2011) Stability analysis of multiple nonequilibrium fixed points in self-consistent electron transport calculations J. Chem. Phys. 135, 174111 (2011) Communication: Orbital instabilities and triplet states from time-dependent density functional theory and longrange corrected functionals J. Chem. Phys. 135, 151103 (2011) All-electron time-dependent density functional theory with finite elements: Time-propagation approach J. Chem. Phys. 135, 154104 (2011) Additional information on J. Chem. Phys. The effect of Cu doping on the properties of small gold cluster cations is investigated in a joint experimental and theoretical study. Temperature-dependent Ar tagging of the clusters serves as a structural probe and indicates no significant alteration of the geometry of Au n + (n = 1-16) upon Cu doping. Experimental cluster-argon bond dissociation energies are derived as a function of cluster size from equilibrium mass spectra and are in the 0.10-0.25 eV range. Near-UV and visible light photodissociation spectroscopy is employed in conjunction with time-dependent density functional theory calculations to study the electronic absorption spectra of Au 4-m Cu m + (m = 0, 1, 2) and their Ar complexes in the 2.00−3.30 eV range and to assign their fragmentation pathways. The tetramers Au 4 + , Au 4 + · Ar, Au 3 Cu + , and Au 3 Cu + · Ar exhibit distinct optical absorption features revealing a pronounced shift of electronic excitations to larger photon energies upon substitution of Au by Cu atoms. The calculated electronic excitation spectra and an analysis of the character of the optical transitions provide detailed insight into the composition-dependent evolution of the electronic structure of the clusters.

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Stability and dissociation pathways of doped Au_nX⁺clusters (X = Y, Er, Nb)

Cited by 41 publications

References 57 publications

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Cage Structure Formation of Singly Doped Aluminum Cluster Cations Al_nTM⁺(TM= Ti, V, Cr)

Copper doping of small gold cluster cations: Influence on geometric and electronic structure

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Stability and dissociation pathways of doped AunX+clusters (X = Y, Er, Nb)

Cited by 41 publications

References 57 publications

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Growth Mechanism and Chemical Bonding in Scandium‐Doped Copper Clusters: Experimental and Theoretical Study in Concert

Cage Structure Formation of Singly Doped Aluminum Cluster Cations AlnTM+(TM= Ti, V, Cr)

Copper doping of small gold cluster cations: Influence on geometric and electronic structure

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Stability and dissociation pathways of doped Au_nX⁺clusters (X = Y, Er, Nb)

Cage Structure Formation of Singly Doped Aluminum Cluster Cations Al_nTM⁺(TM= Ti, V, Cr)