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[摘要]：Electron population terms WrN-3V are evaluated for N = Se, S, and O. Calcns. are performed on HOMO and LUMO constructed by pure at. 4p(Se), 3p(S), and 2p(O) orbitals, employing the 6-311+G(3d) and/or levels. Se4+, Se2+, Se0, and Se2- with the Oh symmetry are called G(A:Se) and HSe+, H2Se, and HSe- with the C or C2v symmetry are named G(B: Se), here [G(A + B: Se) in all]. HOMO and LUMO in G(A + B:N) (N = Se, S, and O) satisfy the conditions of the calcns. for WrN-3V. The WrSe-3V4p, Wrs-3V3p, and WrO-3V2p values correlate well with the corresponding MO energies (EN) for all calcn. levels employed. Plots of WrN-3VHOMO and WrN-3VLUMO vs. Q(N) (N = Se, S, and O) at the HF and MP2 levels are analyzed as two correlations. However, the plots at the DFT level can be analyzed as single correlation. A regression curve is assumed for the anal. Behaviors of WrN-3V clarify how valence orbitals shrink or expand depending on Q(N). The applicability of WrN-3V is examd. to establish a new method that enables us to analyze chem. shifts with the charge effect sep. from others. A utility program derived from the Gaussian 03 (NMRANAL-NH03G) is applied to evaluate WrN-3V and examine the applicability to the NMR anal. |
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