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|Title:||What is the ground electronic state of KO?|
|Authors:||Lee, Edmond P. F.|
Wright, Timothy G.
Coupled cluster calculations
Potential energy surfaces
Energy level crossing
Ab initio calculations
|Publisher:||American Institute of Physics|
|Source:||Journal of chemical physics, 8 Nov. 2002, v. 117, no. 18, p. 8241-8247.|
|Abstract:||High-level, restricted coupled cluster with singles, doubles, and perturbative triples calculations are performed to determine the ground electronic state of KO. In the absence of spin–orbit coupling, we find that the ground state is a ²Σ⁺ state, with a² Π state lying just over 200 cm⁻¹ higher in energy. We ascertain that basis set extension, higher-order correlation energy, mass-velocity, and Darwin relativistic terms do not change this ordering. We then calculate the low-lying Ω states when spin–orbit coupling is turned on. The ²Σ⁺ ₁/₂state undergoes an avoided crossing with the 2Π ₁/₂state, and we therefore designate the ground state as X ½. This state is essentially ²Σ⁺ ₁/₂at short R, but essentially 2Π ₁/₂at long R; there is a corresponding A ½ state with the opposite behavior. These states have significantly different shapes and so spectroscopy from the adiabatic states. Finally, we calculate the dissociation energy D ₒ, of KO as 66±1 kcal mol⁻¹ and derive ΔH[sub f](KO, 0 K) as 13.6±1 kcal mol⁻¹.|
|Rights:||© 2002 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in E. P. F. Lee et al., J. Chem. Phys. 117, 8241 (2002) and may be found at http://link.aip.org/link/?jcp/117/8241.|
|Appears in Collections:||ABCT Journal/Magazine Articles|
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