TY - JOUR
T1 - Anion photoelectron spectroscopy of vanadium-doped cobalt clusters
AU - Pramann, Axel
AU - Koyasu, Kiichirou
AU - Nakajima, Atsushi
AU - Kaya, Koji
PY - 2002/3/21
Y1 - 2002/3/21
N2 - Bimetallic cobalt (Co)-vanadium (V) clusters, ConVm- (n = 4-14, m = 0-2), are investigated using anion photoelectron spectroscopy at 4.66 eV photon energy. Electron affinities (EA) and vertical detachment energies (VDE) are determined, and the electronic structures of V- and V2-doped Con clusters are compared to those of pure Con clusters. Bonding and hybridization effects can be explained using a charge-transfer model. A peak shape analysis confirms the high stability of the Co12V cluster with a most plausible icosahedral structure with the V atom in the cage center. Together with ionization potentials (IP), the electronic structures of the clusters are compared to H2 chemisorption rate coefficients reported previously. Thus, this study completes the investigation of electronic properties and reactivity of the bimetallic ConVm clusters as a function of charge, size, and distribution. Although the reactivity of ConVm reveals a better correlation toward the EA rather than toward IP, no improved correlation is found between promotion energies and reactivity. This result clearly shows that the chemisorption reactivity of the heterogeneous clusters is largely governed by geometric factors.
AB - Bimetallic cobalt (Co)-vanadium (V) clusters, ConVm- (n = 4-14, m = 0-2), are investigated using anion photoelectron spectroscopy at 4.66 eV photon energy. Electron affinities (EA) and vertical detachment energies (VDE) are determined, and the electronic structures of V- and V2-doped Con clusters are compared to those of pure Con clusters. Bonding and hybridization effects can be explained using a charge-transfer model. A peak shape analysis confirms the high stability of the Co12V cluster with a most plausible icosahedral structure with the V atom in the cage center. Together with ionization potentials (IP), the electronic structures of the clusters are compared to H2 chemisorption rate coefficients reported previously. Thus, this study completes the investigation of electronic properties and reactivity of the bimetallic ConVm clusters as a function of charge, size, and distribution. Although the reactivity of ConVm reveals a better correlation toward the EA rather than toward IP, no improved correlation is found between promotion energies and reactivity. This result clearly shows that the chemisorption reactivity of the heterogeneous clusters is largely governed by geometric factors.
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U2 - 10.1021/jp013791f
DO - 10.1021/jp013791f
M3 - Article
AN - SCOPUS:0037149777
VL - 106
SP - 2483
EP - 2488
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 11
ER -