Actions for Spectroscopic Properties of Novel Aromatic Metal Clusters [electronic resource] : NaM4 (M=Al, Ga, In) and their Cations and Anions

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Spectroscopic Properties of Novel Aromatic Metal Clusters [electronic resource] : NaM4 (M=Al, Ga, In) and their Cations and Anions

Published
Washington, D.C. : United States. Dept. of Energy, 2004.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description
PDF-file: 40 pages; size: 0.1 Mbytes
Additional Creators
Lawrence Berkeley National Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The ground and several excited states of metal aromatic clusters, namely NaM4 and NaM₄{sup ±} (M=Al, Ga, In) clusters have been investigated by employing complete activespace self-consistent-field (CASSCF) followed by Multi-reference singles and doubles configuration interaction (MRSDCI) computations that included up to 10 million configurations and other methods. The ground states NaM₄⁻ of aromatic anions are found to be symmetric C{sub 4v} (¹A₁) electronic states with ideal square pyramid geometries. While the ground state of NaIn4 is also predicted to be a symmetric C{sub 4v} (²A₁) square pyramid, the ground state of the NaAl4 cluster is found to have a C{sub 2v} (²A₁) pyramid with a rhombus base and the ground state of NaGa₄ possesses a C{sub 2v} (²A₁) pyramid with a rectangle base. In general these structures exhibit 2 competing geometries, viz., an ideal C{sub 4v} structure and a distorted rhomboidal or rectangular pyramid structure (C{sub 2v}). All of the ground states of the NaM₄⁺ (M= Al, Ga, In) cations are computed to be C{sub 2v} (³A₂) pyramids with rhombus bases. The equilibrium geometries, vibrational frequencies, dissociation energies, adiabatic ionization potentials, adiabatic electron affinities for the electronic states of NaM₄ (M=Al, Ga, In) and their ions are computed and compared with experimental results and other theoretical calculations. On the basis of our computed excited states energy separations, we have tentatively suggested assignments to the observed X and A states in the anion photoelectron spectra of Al₄Na⁻ reported by Li et al. The X state can be assigned to a C{sub 2v} (²A₁) rhomboidal pyramid. The A state observed in the anion spectrum is assigned to the first excited state (²B₁) of the neutral NaAl₄ with the C{sub 4v} symmetry. The assignments of the excited states are consistent with the experimental excitation energies and the previous green's function based methods for the vertical transition energy separations between the X and A bands.
Report Numbers
E 1.99:ucrl-jrnl-203051
ucrl-jrnl-203051
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Note
Published through SciTech Connect.
03/17/2004.
"ucrl-jrnl-203051"
Published in: Journal of Chemical Physics, vol. 120, no. 22, June 8, 2004, pp. 10501 120 22 ISSN 0021-9606; JCPSA6 FT
Zhao, C; Balasubramanian, K.
Funding Information
W-7405-ENG-48
View MARC record | catkey: 14393464