Potential energy surfaces for RhH sub 2 sup +

Journal Article · Thu Sep 05 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100171a027· OSTI ID:5157372

Das, K K; Balasubramanian, K ^[1]

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1. Arizona State Univ., Tempe (United States)

Complete active space multiconfiguration self-consistent-field (CASSCF) calculations followed by multireference singles-plus-doubles configuration interactions (MRSDCI) have been carried out on 12 electronic states of RhH{sup +}{sub 2}. The bending potential energy surfaces of RhH{sup +}{sub 2} reveal that the a{sup 3}F ground state of Rh{sup +} forms a complex with H{sub 2} with a geometry of r{sub e} = 1.737 {Angstrom}, {eta}{sub e} = 27{degrees}, and D{sub e} = 17.5 kcal/mol relative to Rh{sup +}({sup 3}F) + H{sub 2}. The bending potential energy surface of the {sup 1}A{sub 1} state of RhH{sup +}{sub 2} exhibits a double minimum with geometries r{sub e} = 1.592 {Angstrom}, {eta}{sub e} = 32{degrees} and r{sub e} = 1.472 {Angstrom}, {eta}{sub e} = 106.8{degrees} at the CASSCF/MRCI level. The acute angle minimum is 0.63 eV more stable than the obtuse angle minimum. The Rh{sup +}(a{sup 5}F) ion needs to surmount a large barrier for insertion into H{sub 2}. The adiabatic ionization potential for RhH{sub 2} is calculated as 7.4 eV. The hydride complexes of rhodium are used as catalysts for olefin hydrogenation.

• OSTI ID: 5157372
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:18; ISSN JPCHA; ISSN 0022-3654
• Country of Publication: United States
• Language: English

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