Theoretical study of the interaction of benzene with Rh{sup +} and Rh{sub 2}{sup +} cations

Journal Article · Tue Jul 01 04:00:00 EDT 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.474402· OSTI ID:664392

Majumdar, D; Roszak, S; Balasubramanian, K ^[1]

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

Extensive {ital ab initio} calculations have been carried out on the benzene{endash}Rh{sup +} (Rh{sup +}{endash}C{sub 6}H{sub 6}) complex, the Rh{sup +}(C{sub 6}H{sub 6}){sub 2} sandwich complex and the Rh{sub 2}{sup +}{hor_ellipsis} benzene interaction products, viz., Rh{sub 2}{sup +}{endash}C{sub 6}H{sub 6} and Rh{sub 2}{sup +}{endash}C{sub 6}H{sub 4}. The {open_quotes}physisorbed{close_quotes} benzene{endash}Rh{sup +} was found to be in a {sup 3}A{sub 2} state with C{sub 6v} symmetry. The ground state of the Rh{sup +}(C{sub 6}H{sub 6}){sub 2} sandwich complex is {sup 3}A{sub 2} with C{sub 2v} symmetry. Although the optimization of the ground state of the sandwich complex was carried out in C{sub 2v} symmetry, no symmetry breaking distortion in the structure of the benzene moiety was found in the final optimized geometry. The relative strength of binding of benzene with the Rh{sup +} cation in these two complexes has also been compared. The interaction of Rh{sub 2}{sup +} and benzene has been found to favor the formation of two different products consistent with the recent experiment of Bondybey and co-workers. The probability of the formation of the chemisorbed Rh{sub 2}{sup +}C{sub 6}H{sub 4} species with respect to the other cleaved product resulting from the physisorbed Rh{sub 2}{sup +}C{sub 6}H{sub 6} species, benzene{endash}Rh{sup +}, has been discussed in the light of energy calculations. {copyright} {ital 1997 American Institute of Physics.}

• DOE Contract Number: FG02-86ER13558
• OSTI ID: 664392
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 107; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
BENZENE
CATIONS
CHEMICAL BONDS
CHEMICAL REACTIONS
CHEMISORPTION
REACTION INTERMEDIATES
RHODIUM COMPLEXES
RHODIUM IONS