Theoretical studies of CO interaction on Rh{sub 3} cluster

Journal Article · Thu May 01 04:00:00 EDT 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.473682· OSTI ID:565256

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 27-low-lying electronic states of Rh{sub 3}CO with different structures have been investigated. Atop, bridged, and threefold CO orientations with Rh{sub 3} were considered. Complete active space multiconfiguration self-consistent field method (CASMCSCF) followed by large scale multireference singles and doubles configuration interaction (MRSDCI) computations that included up to 2.1 million configurations were used. Three nearly degenerate electronic states were found for the threefold structure around the minimum energy region. At the highest level of theory, the {sup 2}A{sub 2} state prevailed to be the ground state. The assignment of minimum energy states for the atop and bridged structures are unambiguous. The {sup 4}B{sub 2} and {sup 4}B{sub 1} electronic states were found to be the most stable states for these two respective geometries. The nature of the metal{endash}CO bond formation in different states is discussed, and the difference density maps of Rh{sub 3}CO with respect to Rh{sub 3} and COs are presented. The dissociation energies and CO vibrational frequencies have been computed and the results are compared with the available experimental data. {copyright} {ital 1997 American Institute of Physics.}

• DOE Contract Number: FG02-86ER13558
• OSTI ID: 565256
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 106; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
ADSORPTION
ATOM-MOLECULE COLLISIONS
ATOMIC CLUSTERS
CARBON MONOXIDE
CONFIGURATION INTERACTION
DISSOCIATION ENERGY
ELECTRONIC STRUCTURE
RHODIUM
RHODIUM COMPOUNDS
SELF-CONSISTENT FIELD
SORPTIVE PROPERTIES
SURFACE PROPERTIES
VIBRATIONAL STATES