Connectivity atom-property constraints

Ab initio calculations were carried out for all the low-lying non-Rydberg states of the systems N2, 02, NO, Of, and NO+. In N2, for example, there are 102 molecular states that result from nitrogen atoms in the lowest 4S, 2D, and 2P states. These states were all uniformly described using VCI wave functions constructed as described in Section II. Minimum basis, double-f basis and double-f-plus-polarization basis sets were employed for these studies. For the minimum basis-set calculations, which were always carried out first, the VCI wave functions represent full Cl projections with the constraint that the K shells were kept frozen for all states. However, no constraint on the 2og and 2ou orbitals was made since a Cl among these orbitals is necessary to ensure proper description of the hole states in these molecules, such as C3n of N2. The calculations all have the property of asymptotically connecting with the correct atomic states. This computational method has previously been applied, with reliable results, to both closed- and open-shell systems.6 9 11... 

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