Sign reversal of the spin-orbit constant for the C 3Pi(u) state of N2.
Ab initio calculations are performed at the multireference configuration-interaction level of theory on the diagonal spin-orbit functions for the lowest non-Rydberg states of (3)Pi(u) symmetry in molecular nitrogen. Spin-orbit constants deduced from the ab initio results confirm the recent suggestion, based on new experimental results, that the C (3)Pi(u) state of N(2), long known to be regular in the region of its potential-energy curve minimum, becomes inverted at higher energies. By removing the effects of the crossing C(') (3)Pi(u) state, it is shown that A(v) for the C state changes sign from positive to negative near v=8, corresponding to a change in principal molecular-orbital configuration from (1sigma(g))(2)(1sigma(u))(2)(2sigma(g))(2)(2sigma(u))(3sigma(g))(2)(1pi(u))(4)(1pi(g)) to (1sigma(g))(2)(1sigma(u))(2)(2sigma(g))(2)(2sigma(u))(2)(3sigma(g))(1pi(u))(3)(1pi(g))(2) at an internuclear distance near 1.4 A.
Ndome
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Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME FRE 3160 CNRS, 5 Boulevard Descartes, 77454 Marne-La-Vallee, France.
Hochlaf
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Lewis
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Heays
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Gibson
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Lefebvre-Brion
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