ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Potential energy curves and spectroscopic parameters of several electronic states of CoH+ have been calculated using multireference configuration interaction methods. The four lowest-lying states X 4Φ, 1 4Σ−, 1 4Π, and 1 4Δ lie between 0 and 0.6 eV. The 2 4Π state, with a minimum slightly below 2.0 eV at R=2.92 a0, exhibits a second minimum (Re=4.46 a0, Te=2.14 eV) due to an avoided crossing between the Co+ occupations d8 and d7s. Such an interaction is also responsible for the shallow minima predicted for the 2 4Δ and 2 4Φ states. Several doublet states of Σ−, Π, Δ, Φ, and Γ character are bound. Except for 1 2Δ, they are expected to exhibit potential barriers along the dissociation path. All bound states have a d77σ2 configuration (7σ is CoH bonding), with the exception of 1 2Δ which is d8 -like and has a significant dσ(Co) contribution into the metal–hydrogen bond. The sextet states 1 6Δ, 1 6Π, 1 6Σ−, and 1 6Φ are repulsive due to single occupation of 7σ. The dissociation energy De(X 4Φ) of 2.18 eV is in good agreement with experimental estimates. The ionization potential (IP) from X 3Φ (CoH) into X 4Φ(CoH+) (6σ→∞) is calculated to be 7.23 eV, supporting an experimental lower limit of 7.30±0.10 eV for this quantity. The next IPs result from ionization of 3π into 1 4Δ of CoH+ and 1δ into 2 4Π, whereas 7σ ionization is expected to break the CoH bond.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.458258
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