Experimental determination of spin orbital coupling states of O2(-)
Abstract
Electron affinities, Ea, E1 and A1 are reported for the 12 primary X, A-K (27 spin) states of O2(-): KeqT3/2 = (SanQan)(2πmek/h2)3/2exp(Ea/RT) k1 = A1T-1/2exp(-E1/RT). These are obtained from pulsed discharge electron capture detector data by rigorously including literature values and uncertainties in a global non-linear least-squares adjustment. Simple molecular orbital theory predicts 27 bonding and 27 anti-bonding low-lying spin states. For the first time, the positive Ea for the 27 bonding states are reported. The partition function ratios of the negative ion and neutral (SanQan), the A1(X-E) and the spin separations are from fundamental constants. The Ea (in eV) are as follows (with the spin states in brackets): [1.050, 1.070]; [0.915, 0.935]; [0.698, 0.718, 0.746, 0.782]; [0.734, 0.754]; [0.559, 0.587]; 0.518; [0.430, 0.450]; 0.380; 0.354; [0.286, 0.298, 0.318, 0.346]; [0.232, 0.252]; [0.172, 0.184, 0.204, 0.232]. The activation energies (in eV) are as follows: E1(X-C) 1.0; E1(D,E) 1.0, 0.8, 0.6; E1(F-K) 0.12-0.08. The Ea and E1 are used to calculate bonding Herschbach ionic Morse-Person empirical curves.
- Publication:
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Journal of Physics B Atomic Molecular Physics
- Pub Date:
- June 2006
- DOI:
- 10.1088/0953-4075/39/11/001
- Bibcode:
- 2006JPhB...39.2317C