Potential energy surfaces for Ir+H sub 2 and Ir sup + +H sub 2 reactions

Journal Article · Thu Nov 15 04:00:00 EST 1990 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459447· OSTI ID:6286721

Balasubramanian, K; Dai, D ^[1]

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1. Department of Chemistry, Arizona State University, Tempe, Arizona 85287-1604 (USA)

Potential energy surfaces of 10 electronic states of IrH{sub 2} and 12 electronic states of IrH{sup +}{sub 2} are computed. A complete active space multi-configuration self-consistent field (CAS-MCSCF) followed by multireference configuration interaction (MRCI) calculations which included up to 270 000 configurations are employed. In addition spin--orbit effects are studied using the relativistic configuration interaction (RCI) method. It is found that the Ir({sup 2}{ital F}) state inserts spontaneously into H{sub 2} to form a stable IrH{sub 2} molecule in a {sup 2}{ital A}{sub 1} ground state which is 28 kcal/mol more stable than Ir({sup 4}{ital F})+H{sub 2} in the absence of spin--orbit effects. The spin--orbit coupling of the quartet and doublet states provides nonzero transition probability for the insertion of Ir ({sup 4}{ital F}) state into H{sub 2}. The {sup 3}{ital P} state of Ir{sup +} was found to insert spontaneously into H{sub 2} to form the {sup 3}{ital A}{sub 2} ground state of IrH{sup +}{sub 2} which is 30 kcal/mol more stable than Ir{sup +}({sup 5}{ital D})+H{sub 2}.

• DOE Contract Number: FG02-86ER13558
• OSTI ID: 6286721
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 93:10; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ATOMIC IONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CONFIGURATION INTERACTION
COUPLING
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY
HYBRIDIZATION
HYDRIDES
HYDROGEN
HYDROGEN COMPOUNDS
INTERMEDIATE COUPLING
IONS
IRIDIUM
IRIDIUM COMPOUNDS
IRIDIUM HYDRIDES
IRIDIUM IONS
KINETICS
L-S COUPLING
METALS
NONMETALS
PLATINUM METALS
POTENTIAL ENERGY
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS