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

Abstract

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.}

Authors:
;  [1]
  1. Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604 (United States)
Publication Date:
OSTI Identifier:
565256
DOE Contract Number:  
FG02-86ER13558
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 106; Journal Issue: 17; Other Information: PBD: May 1997
Country of Publication:
United States
Language:
English
Subject:
66 PHYSICS; RHODIUM; ATOM-MOLECULE COLLISIONS; SORPTIVE PROPERTIES; CARBON MONOXIDE; ADSORPTION; RHODIUM COMPOUNDS; ELECTRONIC STRUCTURE; VIBRATIONAL STATES; ATOMIC CLUSTERS; SURFACE PROPERTIES; DISSOCIATION ENERGY; CONFIGURATION INTERACTION; SELF-CONSISTENT FIELD

Citation Formats

Majumdar, D, and Balasubramanian, K. Theoretical studies of CO interaction on Rh{sub 3} cluster. United States: N. p., 1997. Web. doi:10.1063/1.473682.
Majumdar, D, & Balasubramanian, K. Theoretical studies of CO interaction on Rh{sub 3} cluster. United States. doi:10.1063/1.473682.
Majumdar, D, and Balasubramanian, K. Thu . "Theoretical studies of CO interaction on Rh{sub 3} cluster". United States. doi:10.1063/1.473682.
@article{osti_565256,
title = {Theoretical studies of CO interaction on Rh{sub 3} cluster},
author = {Majumdar, D and Balasubramanian, K},
abstractNote = {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.}},
doi = {10.1063/1.473682},
journal = {Journal of Chemical Physics},
number = 17,
volume = 106,
place = {United States},
year = {1997},
month = {5}
}