Potential energy surfaces for Rh--CO, Rh--OC, Ir--CO, and Ir--OC interactions

Journal Article · Mon Aug 01 04:00:00 EDT 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.468474· OSTI ID:7180131

Dai, D; Balasubramanian, K ^[1]

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

The potential energy surfaces for eight low-lying electronic states of the Rh--CO and Rh--OC complexes and of the Ir--CO and Ir--OC complexes have been studied using the complete active space multiconfiguration self-consistent field method followed by the multireference singles+doubles configuration interaction calculations which included up to 1.6 million configurations. In addition, spin--orbit effects are included through the relativistic configuration interaction method for the Ir--CO complex. It is found that the Rh([sup 2][ital F]) and Ir([sup 2][ital F]) states react spontaneously with CO to form stable RhCO and IrCO molecules in which the [sup 2][Delta] ground states are 42.4 and 75.1 kcal/mol more stable than Rh([sup 2][ital F])+CO([sup 1][Sigma][sup +]) and Ir([sup 2][ital F])+CO([sup 1][Sigma][sup +]) states, respectively, in the absence of spin--orbit effects. The RhOC and IrOC complexes in the [sup 2][Delta] states were found to be less stable than Rh([sup 4][ital F])+CO([sup 1][Sigma][sup +]) and Ir([sup 4][ital F])+CO([sup 1][Sigma][sup +]), respectively. The nature of the chemical bond is discussed in terms of the wave function composition, and the electronic population analysis.

• DOE Contract Number: FG02-86ER13558
• OSTI ID: 7180131
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 101:3; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664300* -- Atomic & Molecular Physics-- Collision Phenomena-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ADSORPTION
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL BONDS
COMPLEXES
COUPLING
ELEMENTS
ENERGY
ENERGY LEVELS
GROUND STATES
INTERMEDIATE COUPLING
IRIDIUM COMPLEXES
L-S COUPLING
METALS
OXIDES
OXYGEN COMPOUNDS
POTENTIAL ENERGY
RHODIUM COMPLEXES
SORPTION
TRANSITION ELEMENT COMPLEXES