Theoretical study of the electronic states of Rh{sub n}{sup +} (n=3{endash}5)

Journal Article · Sun Feb 01 04:00:00 EST 1998 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.475632· OSTI ID:573877

Majumdar, D; Balasubramanian, K ^[1]

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1. Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604 (United States)

Geometries and energy separations of the various low-lying electronic states of Rh{sub 3}{sup +}, Rh{sub 4}{sup +}, and Rh{sub 5}{sup +} clusters with different structural arrangements have been investigated. The complete active space multiconfiguration self-consistent field method, (CASMCSCF) followed by large scale multireference singles plus doubles configuration interaction (MRSDCI) computations that included up to 1.6 million configurations for Rh{sub 3}{sup +}, 1.5 million configurations for Rh{sub 4}{sup +}, and 2.7 million configurations for Rh{sub 5}{sup +}, were used. Four nearly degenerate electronic states were found for Rh{sub 3}{sup +}. The {sup 6}A{sup {prime}} electronic state of the pyramidal structure of Rh{sub 4}{sup +} was found to be the ground state. Although the {sup 6}A{sup {double_prime}} electronic state of Rh{sub 4}{sup +} with the same geometry was found to be close in energy at the CASMCSCF level, it is 0.5 eV higher at the higher level of theory. Two nearly degenerate electronic states ({sup 5}A{sup {double_prime}} and {sup 5}A{sup {double_prime}}) of the distorted edge capped tetrahedron structure of Rh{sub 5}{sup +} were found as candidates for the ground state of this cluster. Mulliken population analysis has been carried out on these cationic clusters to investigate their bonding properties. {copyright} {ital 1998 American Institute of Physics.}

• OSTI ID: 573877
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 108; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
ATOMIC CLUSTERS
CATIONS
CHEMICAL BONDS
CONFIGURATION INTERACTION
ELECTRONIC STRUCTURE
MOLECULAR STRUCTURE
RHODIUM
SELF-CONSISTENT FIELD