Accurate transition moments between the A 3u+, B3IIg, and B3u- of N2 using multiconfigurational linear response
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Accurate values of the electronic transition moment function for the first positive (A 3u+-B 3II g) and infrared afterglow (B 3IIg-B 33IIg-B13u-) systems of N2 were obtained through multiconfigurational linear response (also known as the multiconfigurational time-dependent Hartree-Fock, MCLR/MCTDHF). MCLR/MCTDHF furnished both excitation energies and transition moments. MCLR/MCTDHF calculations on the first positive system demonstrate the importance of configurations involving the 2g orbital. To obtain accurate values, configurations were chosen with a complete active space of all valence orbitals (2g, 2u, 1u, 3g3u). This is the first MCLR/MCTDHF calculation for molecules as large as first row diatomics in which a complete active space including the entire valence shell is employed. The results are in substantial agreement with accurate theoretical calculations by others and, hence, disagree in their overall behavior with the previously published empirical values. One of our conclusions is that the experimental values for the first positive system far from the equilibrium region are in error. 1988 American Institute of Physics.
